CN110235033B - Composition, film, near-infrared cut filter, solid-state imaging element, image display device, and infrared sensor - Google Patents

Composition, film, near-infrared cut filter, solid-state imaging element, image display device, and infrared sensor Download PDF

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CN110235033B
CN110235033B CN201880008983.XA CN201880008983A CN110235033B CN 110235033 B CN110235033 B CN 110235033B CN 201880008983 A CN201880008983 A CN 201880008983A CN 110235033 B CN110235033 B CN 110235033B
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CN110235033A (en
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森全弘
水野明夫
尾田和也
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Fujifilm Corp
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Abstract

The invention provides a composition capable of producing a film with good stability over time and excellent adhesion to a support or the like. Also provided are a film, a near-infrared cut filter, a solid-state imaging element, an image display device, and an infrared sensor. The composition comprises: a near-infrared ray absorbing compound having a pi-conjugated plane containing a monocyclic or fused aromatic ring; and a compound A having a radical polymerizable ethylenically unsaturated group and a weight average molecular weight of 3000 or more, the compound A containing a repeating unit having a graft chain.

Description

Composition, film, near-infrared cut filter, solid-state imaging element, image display device, and infrared sensor
Technical Field
The present invention relates to a composition, a film, a near-infrared cut filter, a solid-state imaging element, an image display device, and an infrared sensor.
Background
In a video camera, a digital still camera, a mobile phone with a camera function, or the like, a CCD (charge coupled device) or a CMOS (complementary metal oxide semiconductor) is used as a solid-state imaging element for a color image. These solid-state imaging elements use silicon photodiodes having sensitivity to infrared rays in their light receiving portions. Therefore, the visibility correction is sometimes performed using a near infrared ray cut filter.
A near-infrared cut filter is produced using a composition containing a near-infrared absorbing compound or the like. As the near-infrared ray absorbing compound, a compound having a wide pi conjugated plane or the like is used. For example, patent document 1 describes the production of a near-infrared ray cut filter or the like using a pyrrolopyrrole compound.
Prior art documents
Patent document
Patent document 1: japanese laid-open patent publication No. 2009-263614
Disclosure of Invention
Technical problem to be solved by the invention
Near-infrared-absorbing compounds having pi conjugated planes tend to aggregate in the composition through interaction of the pi conjugated planes with each other, and the viscosity of the composition tends to increase with time. Therefore, in recent years, further improvement in the stability over time of a composition containing a near-infrared absorbing compound has been desired.
In addition, in recent years, a film produced using a composition containing a near-infrared absorbing compound is expected to have further improved adhesion to a support. If the adhesion of the film to the support can be improved, for example, in the case of forming a film having a pattern, the peeling of the film or the like at the time of forming the pattern can be suppressed. Therefore, a finer pattern can be formed.
The purpose of the present invention is to provide a composition that can produce a film that has good stability over time and excellent adhesion to a support or the like. Also provided are a film, a near-infrared cut filter, a solid-state imaging element, an image display device, and an infrared sensor.
Means for solving the technical problem
Based on the above situation, the present inventors have conducted extensive studies and as a result, have found that the above object can be achieved by a composition having a structure described below, and have completed the present invention. Thus, the present invention provides the following.
< 1 > a composition comprising:
a near-infrared ray absorbing compound having a pi-conjugated plane containing a monocyclic or fused aromatic ring; and
a compound A having a radical polymerizable ethylenically unsaturated group and a weight average molecular weight of 3000 or more,
compound a comprises a repeat unit with a grafted chain.
< 2 > such as < 1 >, wherein
The radical polymerizable ethylenically unsaturated group of the compound a is at least one selected from the group consisting of a vinyl group, a vinyloxy group, an allyl group, a methallyl group, a (meth) acryloyl group, a styryl group, a cinnamoyl group, and a maleimide group.
Compositions as described under < 3 > such as < 1 > or < 2 >, wherein
The graft chain contains at least one structure selected from the group consisting of a polyester structure, a polyether structure, a poly (meth) acrylic structure, a polyurethane structure, a polyurea structure, and a polyamide structure.
Compositions as described under < 4 > and < 3 >, wherein
The grafted chains comprise a polyester structure.
The composition being < 5 > such as < 1 > to < 4 >, wherein
The weight average molecular weight of the repeating unit having a graft chain is 1000 or more.
The composition being < 6 > such as < 1 > to < 5 >, wherein
The compound a contains a repeating unit having a radical polymerizable ethylenically unsaturated group and a repeating unit having a graft chain.
The composition being < 7 > such as < 1 > to < 6 >, wherein
The compound A comprises a repeating unit represented by the following formula (A-1-1) and a repeating unit represented by the following formula (A-1-2);
[ chemical formula 1]
Figure BDA0002147187970000031
In the formula (A-1-1), X1Denotes the main chain of the repeating unit, L1Represents a single bond or a 2-valent linking group, Y1A group which represents an ethylenically unsaturated group having radical polymerizability;
in the formula (A-1-2), X2Denotes the main chain of the repeating unit, L2Represents a single bond or a 2-valent linking group, W1The graft chain is shown.
The composition being < 8 > such as < 1 > to < 7 >, wherein
Compound a also contains a repeating unit having an acid group.
The composition being < 9 > such as < 1 > to < 8 >, wherein
The amount of the radical polymerizable ethylenically unsaturated group in the compound A is 0.2 to 5.0 mmol/g.
The composition being < 10 > such as < 1 > to < 9 >, wherein
The acid value of the compound A is 20-150 mgKOH/g.
The composition of any one of < 11 > such as < 1 > to < 10 >, wherein
The near-infrared absorbing compound is at least one selected from the group consisting of a pyrrolopyrrole compound, a cyanine compound, a squaric acid compound, a phthalocyanine compound, a naphthalocyanine compound, and a diimmonium compound.
The composition of < 12 > such as < 1 > to < 11 > further contains a color material which transmits infrared rays and shields visible rays.
< 13 > a film obtained from the composition of any one of < 1 > to < 12 >.
< 14 > a near infrared ray cutoff filter having < 13 > said film.
< 15 > a solid-state imaging element having the film < 13 >.
< 16 > an image display device having < 13 > said film.
< 17 > an infrared sensor having < 13 > said film.
Effects of the invention
The present invention can provide a composition that can produce a film that has good stability over time and excellent adhesion to a support or the like. Further, a film, a near-infrared cut filter, a solid-state imaging element, an image display device, and an infrared sensor can be provided.
Drawings
Fig. 1 is a schematic diagram showing an embodiment of an infrared sensor.
The present invention will be described in detail below.
In the present specification, "to" is used to include numerical values before and after the "to" as a lower limit value and an upper limit value.
With regard to labeling of a group (atomic group) in the present specification, a substituted and unsubstituted label is not recorded to include both a group (atomic group) having no substituent and a group (atomic group) having a substituent. For example, "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, "exposure" is not particularly limited, and in addition to exposure using light, drawing using a particle beam such as an electron beam or an ion beam is also included in exposure. Examples of the light used for exposure generally include actinic rays or radiation such as far ultraviolet rays, extreme ultraviolet rays (EUV light), X-rays, and electron beams, which are represented by the bright line spectrum of a mercury lamp or an excimer laser.
In the present specification, "(meth) acrylate" represents both or either of acrylate and methacrylate, "(meth) acrylic acid" represents both or either of acrylic acid and methacrylic acid, and "(meth) acryloyl group" represents both or either of acryloyl group and methacryloyl group.
In the present specification, the weight average molecular weight and the number average molecular weight are defined as styrene equivalent values measured by Gel Permeation Chromatography (GPC).
In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be determined by using HLC-8220GPC (TOSOH CORPORATION), using a column in which TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000 and TOSOH TSKgel Super HZ2000 are connected, and using tetrahydrofuran as a developing solvent, for example.
In the present specification, Me in the chemical formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In the present specification, the near infrared ray refers to light (electromagnetic wave) having a wavelength of 700 to 2500 nm.
In the present specification, the total solid content means the total mass of the components after removing the solvent from all the components of the composition.
In the present specification, the term "step" includes not only an independent step but also an operation expected for the step if the operation cannot be clearly distinguished from other steps.
< composition >
The composition of the present invention is characterized by containing: a near-infrared ray absorbing compound having a pi-conjugated plane containing a monocyclic or fused aromatic ring; and a compound A having a radical polymerizable ethylenically unsaturated group and a weight average molecular weight of 3000 or more, the compound A containing a repeating unit having a graft chain.
The composition of the present invention can produce a film having good stability over time and excellent adhesion to a support or the like. The reason why these effects can be obtained is presumed to be as follows. It is presumed that the compound a approaches the near-infrared ray absorbing compound by the interaction of the radical polymerizable ethylenically unsaturated group of the compound a with the pi-conjugated plane of the near-infrared ray absorbing compound, and the near-infrared ray absorbing compound is present in the composition so as to be encapsulated by the compound a. Further, it is presumed that since the compound a contains a repeating unit having a graft chain, association of the near-infrared absorbing compounds with each other can be suppressed by steric hindrance by the graft chain. Therefore, it is presumed that the dispersibility of the near-infrared absorbing compound can be improved and a composition having excellent stability over time can be obtained. Further, it is presumed that the compound a has a radical polymerizable ethylenically unsaturated group, but the radical polymerizable ethylenically unsaturated group is excellent in reactivity, and therefore, curability of the film can be improved. Further, it is estimated that when the compound a is polymerized in the vicinity of the near infrared ray absorbing compound, the increase in molecular weight due to the polymerization becomes large, and the curability of the film can be further improved. Therefore, it is presumed that the adhesion of the film to the support or the like can be improved. Hereinafter, each component of the composition of the present invention will be described.
Near infrared ray absorbing compound
The composition of the present invention contains a near-infrared absorbing compound which is a compound having a pi-conjugated plane including a monocyclic or fused aromatic ring. In the present invention, the near-infrared-absorbing compound preferably has absorption in the near-infrared region (preferably, in the range of 700 to 1300nm, and more preferably, in the range of 700 to 1000 nm).
Since the near-infrared ray absorbing compound in the present invention has a pi conjugated plane including a monocyclic or condensed ring aromatic ring, a J association of the near-infrared ray absorbing compound is easily formed in the film by the interaction between the aromatic rings on the pi conjugated plane of the near-infrared ray absorbing compound, and a film having excellent near-infrared region spectral characteristics can be formed.
In the present invention, the near-infrared ray absorbing compound may be a pigment (also referred to as a near-infrared ray absorbing pigment) or a dye (also referred to as a near-infrared ray absorbing dye).
The number of atoms other than hydrogen constituting the pi-conjugated plane of the near-infrared ray absorbing compound is preferably 14 or more, more preferably 20 or more, still more preferably 25 or more, and particularly preferably 30 or more. The upper limit is, for example, preferably 80 or less, and more preferably 50 or less.
The pi conjugated plane of the near-infrared ray absorbing compound preferably contains 2 or more monocyclic or fused aromatic rings, more preferably 3 or more aromatic rings, further 4 or more aromatic rings, and particularly preferably 5 or more aromatic rings. The upper limit is preferably 100 or less, more preferably 50 or less, and further 30 or less. Examples of the aromatic ring include a benzene ring, a naphthalene ring, a pentalene ring, an indene ring, an azulene ring, a heptalene ring, an indacene ring, a perylene ring, a pentacene ring, a quartilene (quaterrylene) ring, an acenaphthylene ring, a phenanthrene ring, an anthracene ring, a tetracene ring, a perylene ring, a base, a,
Figure BDA0002147187970000061
(chrysene) ring, triphenylene ring, fluorene ring, pyridine ring, quinoline ring, isoquinoline ring, imidazole ring, benzimidazole ring, pyrazole ring, thiazole ring, benzothiazole ring, triazole ring, benzotriazole ring, oxazole ring, benzoxazole ring, imidazoline ring, pyrazine ring, quinoxaline ring, pyrimidine ring, quinazoline ring, pyridazine ring, triazine ring, pyrrole ring, indole ring, isoindole ring, carbazole ring, and a condensed ring having these rings.
The near infrared ray absorbing compound is preferably a compound having a maximum absorption wavelength in a wavelength range of 700 to 1000 nm. In the present specification, the phrase "having a maximum absorption wavelength in a wavelength range of 700 to 1000 nm" means that the absorption spectrum in a solution of a near-infrared absorbing compound has a wavelength indicating the maximum absorbance in a wavelength range of 700 to 1000 nm. Examples of the measuring solvent used for measuring the absorption spectrum in the solution of the near-infrared absorbing compound include chloroform, methanol, dimethyl sulfoxide, ethyl acetate, and tetrahydrofuran. In the case of a compound dissolved in chloroform, chloroform was used as a solvent for measurement. When the compound is a compound insoluble in chloroform, methanol is used. In the case where neither chloroform nor methanol is soluble, dimethyl sulfoxide is used.
The near infrared ray absorbing compound preferably has a maximum absorption wavelength in a wavelength range of 700 to 1000nm, and is a compound having a ratio Amax/A550 of an absorbance Amax at the maximum absorption wavelength to an absorbance A550 at a wavelength of 550nm of 50 to 500. Amax/A550 in the near-infrared absorbing compound is preferably 70 to 450, more preferably 100 to 400. According to this embodiment, a film excellent in visible transparency and near-infrared shielding properties can be easily produced. The absorbance a550 at a wavelength of 550nm and the absorbance Amax at a maximum absorption wavelength are values obtained from an absorption spectrum in a solution of the near-infrared absorbing compound.
In the present invention, it is also preferable to use at least two compounds having different maximum absorption wavelengths as the near-infrared ray absorbing compound. According to this embodiment, the waveform of the absorption spectrum of the film is broader than that in the case where one near-infrared ray absorbing compound is used, and near-infrared rays in a wide wavelength range can be blocked. When at least two compounds having different maximum absorption wavelengths are used, at least a1 st near infrared ray absorption compound having a maximum absorption wavelength in a wavelength range of 700 to 1000nm and a2 nd near infrared ray absorption compound having a maximum absorption wavelength in a wavelength range of 700 to 1000nm on a shorter wavelength side than the maximum absorption wavelength of the 1 st near infrared ray absorption compound are contained, and the difference between the maximum absorption wavelength of the 1 st near infrared ray absorption compound and the maximum absorption wavelength of the 2 nd near infrared ray absorption compound is preferably 1 to 150 nm.
In the present invention, the near-infrared ray absorbing compound is preferably at least one selected from the group consisting of a pyrrolopyrrole compound, a cyanine compound, a squaric acid compound, a phthalocyanine compound, a naphthalocyanine compound, a quartorene compound, a merocyanine compound, a croconic acid compound, an oxonol compound, a diimmonium compound, a dithiol compound, a triarylmethane compound, a pyrromethene compound, a methine compound, an anthraquinone compound and a dibenzofuranone compound, more preferably at least one selected from the group consisting of a pyrrolopyrrole compound, a cyanine compound, a squaric acid compound, a phthalocyanine compound, a naphthalocyanine compound and a diimmonium compound, still more preferably at least one selected from the group consisting of a pyrrolopyrrole compound, a cyanine compound and a squaric acid compound, and particularly preferably a pyrrolopyrrole compound. Examples of the diimmonium compound include those described in japanese unexamined patent publication No. 2008-528706, which are incorporated herein by reference. Examples of the phthalocyanine compound include compounds described in paragraph 0093 of Japanese patent laid-open No. 2012 and 077153, oxytitanium phthalocyanine described in Japanese patent laid-open No. 2006 and 343631, and compounds described in paragraphs 0013 to 0029 of Japanese patent laid-open No. 2013 and 195480, and these contents are incorporated in the present specification. Examples of the naphthalocyanine compound include the compounds described in paragraph 0093 of Japanese patent application laid-open No. 2012-077153, the contents of which are incorporated herein. The cyanine compound, phthalocyanine compound, naphthalocyanine compound, diimmonium compound and squaric acid compound may be the compounds described in paragraphs 0010 to 0081 of jp 2010-111750 a, and the contents thereof are incorporated herein. Further, the cyanine compound can be referred to, for example, as "functional pigment, daghui/pindang/north tail light/hinoki constant red, Kodansha Scientific ltd", and this is incorporated herein. Further, as the near-infrared absorbing compound, the compounds described in japanese patent application laid-open No. 2016-146619 can be used, and the contents thereof are incorporated in the present specification.
As the pyrrolopyrrole compound, a compound represented by the formula (PP) is preferable.
[ chemical formula 2]
Figure BDA0002147187970000081
In the formula, R1aAnd R1bEach independently represents alkyl, aryl or heteroaryl, R2And R3Each independently represents a hydrogen atom or a substituent, R2And R3May be bonded to each other to form a ring, R4Each independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -BR4AR4BOr a metal atom, R4Can be substituted with one or more groups selected from R1a、R1bAnd R3At least 1 of which is covalently or coordinately bound, R4AAnd R4BEach independently represents a substituent. The details of formula (PP) can be found in Japanese patent laid-open publication No. 2009-263614Paragraphs 0017 to 0047, paragraphs 0011 to 0036 of Japanese patent application laid-open No. 2011-068731, and paragraphs 0010 to 0024 of International publication No. WO2015/166873, which are incorporated herein by reference.
R1aAnd R1bPreferably each independently is aryl or heteroaryl, more preferably aryl. And, R1aAnd R1bThe alkyl group, aryl group and heteroaryl group may have a substituent or may be unsubstituted. Examples of the substituent include an alkoxy group, a hydroxyl group, a halogen atom, a cyano group, a nitro group and an-OCOR group11、-SOR12、-SO2R13And the like. R11～R13Each independently represents a hydrocarbon group or a heterocyclic group. Examples of the substituent include those described in paragraphs 0020 to 0022 of Japanese patent laid-open publication No. 2009-263614. Among these, preferred as the substituent are alkoxy, hydroxy, cyano, nitro, -OCOR11、-SOR12、-SO2R13. As a group consisting of R1a、R1bThe group represented by (A) is preferably an aryl group having an alkoxy group having a branched alkyl group as a substituent, (B) is an aryl group having a hydroxyl group as a substituent, or is a group represented by-OCOR11The group represented is an aryl group having a substituent. The number of carbon atoms of the branched alkyl group is preferably 3 to 30, more preferably 3 to 20.
Preferably R2And R3At least one of them is an electron-withdrawing group, more preferably R2Represents an electron withdrawing group (preferably cyano group), R3Represents a heteroaryl group. The heteroaryl group is preferably a 5-membered ring or a 6-membered ring. The heteroaryl group is preferably a single ring or a condensed ring, preferably a single ring or a condensed ring having a condensed number of 2 to 8, and more preferably a single ring or a condensed ring having a condensed number of 2 to 4. The number of hetero atoms constituting the heteroaryl group is preferably 1 to 3, more preferably 1 to 2. Examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom. The heteroaryl group preferably has 1 or more nitrogen atoms. 2R in the formula (PP)2May be the same as or different from each other. And 2R in the formula (PP)3May be the same as or different from each other.
R4Preferably a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group or a substituted or unsubstituted-BR group4AR4BMore preferably a hydrogen atom, an alkyl group, an aryl group or a group represented by-BR4AR4BThe group represented by (A) is more preferably represented by-BR4AR4BThe group shown. As R4AAnd R4BThe substituent represented is preferably a halogen atom, an alkyl group, an alkoxy group, an aryl group or a heteroaryl group, more preferably an alkyl group, an aryl group or a heteroaryl group, and particularly preferably an aryl group. These groups may further have a substituent. 2R in the formula (PP)4May be the same as or different from each other.
Specific examples of the compound represented by the formula (PP) include the following compounds. In the following structural formula, Me represents a methyl group, and Ph represents a phenyl group. Examples of the pyrrolopyrrole compound include compounds described in paragraphs 0016 to 0058 of Japanese patent application laid-open No. 2009-263614, compounds described in paragraphs 0037 to 0052 of Japanese patent application laid-open No. 2011-068731, and compounds described in paragraphs 0010 to 0033 of International publication WO2015/166873, and the contents of these are incorporated in the present specification.
[ chemical formula 3]
Figure BDA0002147187970000101
The squarylium compound is preferably a compound represented by the following formula (SQ).
[ chemical formula 4]
Figure BDA0002147187970000102
In the formula (SQ), A1And A2Each independently represents an aryl group, a heteroaryl group or a group represented by the formula (A-1);
[ chemical formula 5]
Figure BDA0002147187970000111
In the formula (A-1), Z1Denotes the formation of a nitrogen-containing heterocycleOf a nonmetallic atom group of R2Represents an alkyl group, an alkenyl group or an aralkyl group, d represents 0 or 1, and the wavy line represents a connecting bond. The details of the formula (SQ) can be found in paragraphs 0020 to 0049 of Japanese patent application laid-open No. 2011-208101, which is incorporated herein by reference.
In the formula (SQ), the cation is present in an unmanaged form as follows.
[ chemical formula 6]
Figure BDA0002147187970000112
Specific examples of the squarylium compound include the following compounds. The squaric acid compound includes the compounds described in paragraphs 0044 to 0049 of jp 2011-208101 a, which is incorporated herein by reference.
[ chemical formula 7]
Figure BDA0002147187970000113
The cyanine compound is preferably a compound represented by formula (C).
Formula (C)
[ chemical formula 8]
Figure BDA0002147187970000121
In the formula, Z1And Z2Each independently a non-metallic radical forming a 5-or 6-membered nitrogen-containing heterocycle which may be fused,
R101and R102Each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group,
L1denotes a methine chain having an odd number of methines,
a and b are each independently 0 or 1,
in the case where a is 0, the carbon atom is double-bonded to the nitrogen atom, and in the case where b is 0, the carbon atom is single-bonded to the nitrogen atom,
when the site represented by Cy in the formula is a cation part, X is1Represents an anion, c represents a number necessary for charge balance, and X represents a site represented by Cy in the formula as an anion portion1And c represents a number necessary for charge balance, and when the charge at the site represented by Cy in the formula is neutralized within the molecule, c is 0.
Examples of the cyanine compound include compounds described in paragraphs 0044 to 0045 of Japanese patent laid-open No. 2009-108267, compounds described in paragraphs 0026 to 0030 of Japanese patent laid-open No. 2002-194040, compounds described in Japanese patent laid-open No. 2015-172004, compounds described in Japanese patent laid-open No. 2015-172102, and compounds described in Japanese patent laid-open No. 2008-088426, and the contents thereof are incorporated herein.
In the present invention, commercially available products can also be used as the near-infrared absorbing compound. Examples thereof include SDO-C33(ARIMOTO CHEMICAL CO., manufactured by LTD.), EX Color IR-14, EX Color IR-10A, EX Color TX-EX-801B, EX Color TX-EX-805K (NIPPON SHOKUBAI CO., manufactured by LTD.), Shigenox NIA-8041, Shigenox NIA-8042, Shigenox NIA-814, Shigenox NIA-820, Shigenox NIA-839(Hakko CHEMICAL Co., manufactured by Ltd., manufactured by L.), Epolite V-63, Eplight 3801, Eplight 3036(Epolin, manufactured by Inc.), PRO-JET825LDI (manufactured by Fujifilm Corporation), NK-3027, NK-5060(Hayashibara Co., manufactured by Ltd., manufactured by YKR., manufactured by Mitsui, etc.).
In the composition of the present invention, the content of the near infrared ray absorbing compound is preferably 10 to 90% by mass based on the total solid content of the composition. The lower limit is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, and particularly preferably 45% by mass or more. The upper limit of the content of the near-infrared ray absorbing compound is preferably 80% by mass or less, more preferably 70% by mass or less, and further preferably 65% by mass or less.
In the composition of the present invention, the content of the near infrared ray absorbing compound is preferably 100 to 500 parts by mass with respect to 100 parts by mass of the compound a described later.
In the present invention, only one kind of near-infrared absorbing compound may be used, or two or more kinds thereof may be used. When two or more kinds are used, the total amount thereof is preferably within the above range.
Other near infrared ray absorbent
The composition of the present invention may contain a near-infrared ray absorber (also referred to as another near-infrared ray absorber) other than the near-infrared ray absorbing compound. Examples of the other near-infrared absorber include inorganic pigments (inorganic particles). The shape of the inorganic pigment is not particularly limited, and may be a flake, a line or a tube, regardless of the spherical shape or the non-spherical shape. As the inorganic pigment, metal oxide particles or metal particles are preferable. Examples of the metal oxide particles include Indium Tin Oxide (ITO) particles, Antimony Tin Oxide (ATO) particles, zinc oxide (ZnO) particles, Al-doped zinc oxide (Al-doped ZnO) particles, and fluorine-doped tin dioxide (F-doped SnO)2) Particulate, niobium doped titanium dioxide (Nb doped TiO)2) Particles, and the like. Examples of the metal particles include silver (Ag) particles, gold (Au) particles, copper (Cu) particles, and nickel (Ni) particles. Further, as the inorganic pigment, a tungsten oxide compound can also be used. The tungsten oxide-based compound is preferably cesium tungsten oxide. For details of the tungsten oxide-based compound, reference can be made to paragraph 0080 of Japanese patent application laid-open No. 2016-006476, which is incorporated herein by reference.
When the composition of the present invention contains another near-infrared ray absorbent, the content of the other near-infrared ray absorbent is preferably 0.01 to 50% by mass based on the total solid content of the composition. The lower limit is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more. The upper limit is preferably 30% by mass or less, and more preferably 15% by mass or less.
The content of the other near-infrared ray absorber in the total mass of the near-infrared ray absorbing compound and the other near-infrared ray absorber is preferably 1 to 99% by mass. The upper limit is preferably 80% by mass or less, more preferably 50% by mass or less, and still more preferably 30% by mass or less.
The composition of the present invention preferably contains substantially no near-infrared absorber. The fact that the near-infrared absorbent is substantially not contained means that the content of the near-infrared absorbent in the total mass of the near-infrared absorbent compound and the near-infrared absorbent is preferably 0.5 mass% or less, more preferably 0.1 mass% or less, and further preferably that the near-infrared absorbent is not contained.
< Compound A >)
The composition of the present invention contains a compound A having a repeating unit of a graft chain and containing an ethylenically unsaturated group having radical polymerizability, and having a weight average molecular weight (Mw) of 3000 or more. In the present invention, the compound A can also be used as a dispersant.
The weight average molecular weight of the compound A is 3000 or more, preferably 3000 to 50,000, more preferably 7000 to 40,000, and further preferably 10000 to 30000. When the weight average molecular weight of the compound a is 3000 or more, the dispersibility of the light-shielding material or the like is good.
The radical polymerizable ethylenically unsaturated group of the compound a is preferably a vinyl group, a vinyloxy group, an allyl group, a methallyl group, a (meth) acryloyl group, a styryl group, a cinnamoyl group, or a maleimide group, more preferably a (meth) acryloyl group, a styryl group, or a maleimide group, still more preferably a (meth) acryloyl group, and particularly preferably an acryloyl group. The (meth) acryloyl group is a group having particularly excellent reactivity and further small steric hindrance, and therefore easily interacts with the pi conjugated plane of the near infrared ray absorbing compound, and the effect of the present invention can be more remarkably obtained.
The amount of the radical polymerizable ethylenically unsaturated group (hereinafter, also referred to as "C ═ C value") of the compound a is preferably 0.2 to 5.0 mmol/g. The upper limit is more preferably 4.0mmol/g or less, and still more preferably 3.0mmol/g or less. The lower limit is more preferably 0.3mmol/g or more. The C ═ C value of compound a is a value indicating the molar amount of C ═ C groups per 1g of solid content of compound a. The C ═ C value of compound a can be calculated from the following formula by extracting the low-molecular component (a) at the C ═ C base position (for example, methacrylic acid in P-1 and acrylic acid in P-2 described later) from compound a by alkali treatment and measuring the content thereof by High Performance Liquid Chromatography (HPLC). When the C ═ C group site cannot be extracted from compound a by the alkali treatment, a value measured by an NMR method (nuclear magnetic resonance) is used.
C-value [ mmol/g ] of compound a ═ (content of low-molecular component (a) [ ppm ]/molecular weight of low-molecular component (a) [ g/mol ])/(weighed value of compound a [ g ] × (solid content concentration of compound a [ mass% ]/100) × 10
In the compound a, it is preferable that the side chain of the repeating unit has a radical polymerizable ethylenically unsaturated group. That is, the compound A preferably contains a repeating unit represented by the following formula (A-1-1).
[ chemical formula 9]
Figure BDA0002147187970000151
In the formula (A-1-1), X1Denotes the main chain of the repeating unit, L1Represents a single bond or a 2-valent linking group, Y1Represents a group having a radical polymerizable ethylenically unsaturated group.
In the formula (A-1-1), as X1The main chain of the repeating unit is not particularly limited. The linking group is not particularly limited as long as it is a known linking group formed from a polymerizable monomer. For example, a poly (meth) acrylic linking group, a polyalkylene imine linking group, a polyester linking group, a polyurethane linking group, a polyurea linking group, a polyamide linking group, a polyether linking group, a polystyrene linking group, and the like are mentioned, and from the viewpoint of availability of raw materials or production suitability, a poly (meth) acrylic linking group and a polyalkylene imine linking group are preferable, and a (meth) acrylic linking group is more preferable.
In the formula (A-1-1), as L1The 2-valent linking group includes an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an alkyleneoxy group (preferably an alkyleneoxy group having 1 to 12 carbon atoms), an oxyalkylene carbonyl group (preferably an oxyalkylene carbonyl group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO2-、-CO-、-O-、-COO-、OCO-, -S-, and a combination of 2 or more of these. The alkylene group, the alkylene group of the alkyleneoxy group, and the alkylene group of the oxyalkylene carbonyl group may be linear, branched, or cyclic, and preferably linear or branched. The alkylene group, the alkylene group in the alkyleneoxy group, and the alkylene group in the oxyalkylene carbonyl group may have a substituent or may be unsubstituted. Examples of the substituent include a hydroxyl group and an alkoxy group, and a hydroxyl group is preferable from the viewpoint of production applicability.
In the formula (A-1-1), Y1Examples of the radical polymerizable ethylenically unsaturated group include groups containing at least one selected from a vinyl group, a vinyloxy group, an allyl group, a methallyl group, (meth) acryloyl group, a styryl group, a cinnamoyl group, and a maleimide group, with a (meth) acryloyl group, a styryl group, and a maleimide group being preferred, a (meth) acryloyl group being more preferred, and an acryloyl group being even more preferred.
Specific examples of the repeating unit represented by the formula (A-1-1) include a repeating unit represented by the following formula (A-1-1a), a repeating unit represented by the following formula (A-1-1b), and the like.
[ chemical formula 10]
Figure BDA0002147187970000161
In the formula (A-1-1a), Ra1～Ra3Each independently represents a hydrogen atom or an alkyl group, Qa1represents-CO-, -COO-, -OCO-, -CONH-, or phenylene, L1Represents a single bond or a 2-valent linking group, Y1Represents a group having a radical polymerizable ethylenically unsaturated group. Ra1～Ra3The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 3, and still more preferably 1. Qa1preferably-COO-or-CONH-, and more preferably-COO-.
In the formula (A-1-1b), Ra10And Ra11Each independently represents a hydrogen atom or an alkyl group, m1 represents an integer of 1 to 5, L1Represents a single bond or a 2-valent linking group, Y1Means having free radical polymerizationA group of linear ethylenically unsaturated groups. Ra10And Ra11The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 3.
In the present invention, the graft chain in the compound a means a polymer chain extending by branching from the main chain of the repeating unit. The length of the graft chain is not particularly limited, but when the graft chain is longer, the steric repulsion effect is increased, and the dispersibility of the near-infrared ray absorbing compound can be improved. The number of atoms other than hydrogen atoms in the graft chain is preferably 40 to 10000, more preferably 50 to 2000, and still more preferably 60 to 500.
The graft chain preferably includes at least one structure selected from a polyester structure, a polyether structure, a poly (meth) acrylic structure, a polyurethane structure, a polyurea structure, and a polyamide structure, more preferably includes at least one structure selected from a polyester structure, a polyether structure, and a poly (meth) acrylic structure, and further preferably includes a polyester structure. The polyester structure may be represented by the following formula (G-1), formula (G-4) or formula (G-5). The polyether structure may be represented by the following formula (G-2). Further, examples of the poly (meth) acrylic structure include a structure represented by the following formula (G-3).
[ chemical formula 11]
Figure BDA0002147187970000171
In the above formula, RG1And RG2Each independently represents an alkylene group. As a group consisting of RG1And RG2The alkylene group is not particularly limited, and is preferably a linear or branched alkylene group having 1 to 20 carbon atoms, more preferably a linear or branched alkylene group having 2 to 16 carbon atoms, and still more preferably a linear or branched alkylene group having 3 to 12 carbon atoms.
In the above formula, RG3Represents a hydrogen atom or a methyl group.
In the above formula, QG1represents-O-or-NH-, LG1Represents a single bondOr a 2-valent linking group. Examples of the 2-valent linking group include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an alkyleneoxy group (preferably an alkyleneoxy group having 1 to 12 carbon atoms), an oxyalkylene carbonyl group (preferably an oxyalkylene carbonyl group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -C2-, -CO-, -O-, -COO-, OCO-, -S-, and a combination of 2 or more of these.
RG4Represents a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkyl sulfide group, an aryl sulfide group, and a heteroaryl sulfide group.
For example, when the graft chain contains a polyester structure, it may contain only one polyester structure, and RG1Two or more polyester structures different from each other may be contained. And, when the graft chain contains a polyether structure, it may contain only one polyether structure, and R isG2Two or more polyether structures different from each other may be contained. And, when the graft chain comprises a poly (meth) acrylic structure, it may comprise only one poly (meth) acrylic structure and is selected from RG3、QG1、LG1And RG4At least one of the (b) may comprise two or more poly (meth) acrylic structures different from each other.
The terminal structure of the graft chain is not particularly limited. May be a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkyl sulfide group, an aryl sulfide group, and a heteroaryl sulfide group. Among them, from the viewpoint of improving the dispersibility of the near-infrared absorbing compound, a group having a steric repulsion effect is preferable, and an alkyl group or an alkoxy group having 5 to 24 carbon atoms is more preferable. The alkyl group and the alkoxy group may be linear, branched or cyclic, and are preferably linear or branched.
In the present invention, the graft chain is preferably a structure represented by the following formula (G-1a), formula (G-2a), formula (G-3a), formula (G-4a) or formula (G-5 a).
[ chemical formula 12]
Figure BDA0002147187970000181
In the above formula, RG1And RG2Each independently represents an alkylene group, RG3Represents a hydrogen atom or a methyl group, QG1represents-O-or-NH-, LG1Represents a single bond or a 2-valent linking group, RG4Represents a hydrogen atom or a substituent, W100Represents a hydrogen atom or a substituent. n1 to n5 each independently represent an integer of 2 or more. With respect to RG1～RG4、QG1、LG1The meaning of which is the same as that of R specified in the formulae (G-1) to (G-5)G1～RG4、QG1、LG1The same meanings as defined above, and the same preferred ranges.
In the formulae (G-1a) to (G-5a), W100Substituents are preferred. Examples of the substituent include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkyl sulfide group, an aryl sulfide group, and a heteroaryl sulfide group. Among them, from the viewpoint of improving the dispersibility of the near-infrared absorbing compound, a group having a steric repulsion effect is preferable, and an alkyl group or an alkoxy group having 5 to 24 carbon atoms is more preferable. The alkyl group and the alkoxy group may be linear, branched or cyclic, and are preferably linear or branched.
In the formulae (G-1a) to (G-5a), n1 to n5 each independently represent an integer of preferably 2 to 100, more preferably 2 to 80, and still more preferably 8 to 60.
In the formula (G-1a), R in each repeating unit when n1 is 2 or moreG1May be the same as or different from each other. And when R isG1When two or more different kinds of repeating units are contained, the arrangement of the respective repeating units is not particularly limited, and may be any of random, cross, and block. The same applies to the formulae (G-2a) to (G-5 a).
Examples of the repeating unit having a graft chain include a repeating unit represented by the following formula (A-1-2).
[ chemical formula 13]
Figure BDA0002147187970000191
In the formula (A-1-2), X2Denotes the main chain of the repeating unit, L2Represents a single bond or a 2-valent linking group, W1The graft chain is shown.
As X in the formula (A-1-2)2As the main chain of the repeating unit, X in the formula (A-1-1)1The preferable range is the same as in the above-described configuration. As L in the formula (A-1-2)2Examples of the 2-valent linking group include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO2-, -CO-, -O-, -COO-, OCO-, -S-, and a combination of 2 or more of these. As W in the formula (A-1-2)1Examples of the graft chain include the graft chains described above.
Specific examples of the repeating unit represented by the formula (A-1-2) include a repeating unit represented by the following formula (A-1-2a), a repeating unit represented by the following formula (A-1-2b), and the like.
[ chemical formula 14]
Figure BDA0002147187970000192
In the formula (A-1-2a), Rb1～Rb3Each independently represents a hydrogen atom or an alkyl group, Qb1represents-CO-, -COO-, -OCO-, -CONH-, or phenylene, L2Represents a single bond or a 2-valent linking group, W1The graft chain is shown. Rb1～Rb3The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 3, and still more preferably 1. Qb1preferably-COO-or-CONH-, and more preferably-COO-.
In the formula (A-1-2b), Rb10And Rb11Each independently represents a hydrogen atom or an alkyl group, m2 represents an integer of 1 to 5, L2Represents a single bond or a 2-valent linking group, W1The graft chain is shown. Rb10And Rb11Carbon of alkyl group represented byThe number of atoms is preferably 1 to 10, more preferably 1 to 3.
In the compound a, the weight average molecular weight (Mw) of the repeating unit having a graft chain is preferably 1000 or more, more preferably 1000 to 10000, and further preferably 1000 to 7500. In the present invention, the weight average molecular weight of the repeating unit having a graft chain is a value calculated from the weight average molecular weight of the raw material monomer used in the polymerization of the repeating unit. For example, a repeating unit having a graft chain can be formed by polymerizing a macromonomer. The macromonomer is a polymer compound having a polymerizable group introduced into a polymer terminal. When the macromonomer is used to form the repeating unit having a graft chain, the weight average molecular weight of the macromonomer corresponds to the repeating unit having a graft chain.
The compound a preferably contains a repeating unit having a radical polymerizable ethylenically unsaturated group and a repeating unit having a graft chain. In the compound a, the repeating unit having a radical polymerizable ethylenically unsaturated group is preferably contained in an amount of 10 to 80 mol%, more preferably 20 to 70 mol%, based on the total repeating units of the compound a. In the compound a, the repeating unit having a graft chain is preferably contained in an amount of 1.0 to 60 mol%, more preferably 1.5 to 50 mol%, based on the total repeating units of the compound a.
Compound a preferably also comprises a repeating unit having an acid group. The compound a further contains a repeating unit having an acid group, whereby the dispersibility of the near infrared ray absorbing compound can be further improved. Further, the developability can be improved. Examples of the acid group include a carboxyl group, a sulfo group, and a phosphate group.
Examples of the repeating unit having an acid group include a repeating unit represented by the following formula (A-1-3).
[ chemical formula 15]
Figure BDA0002147187970000201
In the formula (A-1-3), X3Denotes the main chain of the repeating unit, L3Represents a single bond or a 2-valent linking group A1Represents an acid group.
As X in the formula (A-1-3)3As the main chain of the repeating unit, X in the formula (A-1-1)1The preferable range is the same as in the above-described configuration.
As L in the formula (A-1-3)3The 2-valent linking group includes an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an alkenylene group (preferably an alkenylene group having 2 to 12 carbon atoms), an alkyleneoxy group (preferably an alkyleneoxy group having 1 to 12 carbon atoms), an oxyalkylene carbonyl group (preferably an oxyalkylene carbonyl group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -2-, -CO-, -O-, -COO-, OCO-, -S-, and a combination of 2 or more of these. The alkylene group, the alkylene group of the alkyleneoxy group, and the alkylene group of the oxyalkylene carbonyl group may be linear, branched, or cyclic, and preferably linear or branched. The alkylene group, the alkylene group in the alkyleneoxy group, and the alkylene group in the oxyalkylene carbonyl group may have a substituent or may be unsubstituted. Examples of the substituent include a hydroxyl group and the like.
As A in the formula (A-1-3)1Examples of the acid group include a carboxyl group, a sulfo group and a phosphate group.
Specific examples of the repeating unit represented by the formula (A-1-3) include a repeating unit represented by the following formula (A-1-3a), a repeating unit represented by the following formula (A-1-3b), and the like.
[ chemical formula 16]
Figure BDA0002147187970000211
In the formula (A-1-3a), Rc1～Rc3Each independently represents a hydrogen atom or an alkyl group, Qc1represents-CO-, -COO-, -OCO-, -CONH-, or phenylene, L3Represents a single bond or a 2-valent linking group A1Represents an acid group. Rc1～Rc3The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 3, and still more preferably 1. Qc1preferably-COO-or-CONH-, and more preferably-COO-.
In the formula (A-1-3b), Rc10And Rc11Each independently represents a hydrogen atom or an alkyl group, m3 represents an integer of 1 to 5, L3Represents a single bond or a 2-valent linking group A1Represents an acid group. Rc10And Rc11The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 3.
The repeating unit represented by the formula (A-1-3a) is more preferably a repeating unit represented by the following formula (A-1-3 a-1).
[ chemical formula 17]
Figure BDA0002147187970000221
In the formula (A-1-3a-1), Rc1～Rc3Each independently represents a hydrogen atom or an alkyl group, Qc1represents-CO-, -COO-, -OCO-, -CONH-, or phenylene, L10Represents a single bond or alkylene group, L11Represents a single bond, -O-, -S-, -NH-, -CO-, -OCO-or-COO-, Rc4Represents an alkylene group or an arylene group, and p represents an integer of 0 to 5. Wherein, when p is 0, L11is-COO-, or L10And L11Is a single bond and Qc1is-COO-.
In the formula (A-1-3a-1), Rc1～Rc3The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 3, and still more preferably 1. Qc1preferably-COO-or-CONH-, and more preferably-COO-.
In the formula (A-1-3a-1), L10The number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 5. The alkylene group may be linear, branched or cyclic, and is preferably linear or branched, and more preferably linear. L is10Preferably a single bond.
In the formula (A-1-3a-1), L11Preferably a single bond or-OCO-, more preferably a single bond.
In the formula (A-1-3a-1), Rc4Preferably an alkylene group. The number of carbon atoms of the alkylene group is preferably 1 to 12, more preferably 1 to 8, further preferably 2 to 8, and particularly preferably 2 to 6. Rc4Alkylene of (A) to (B)The group may be linear, branched or cyclic, preferably linear or branched, more preferably linear.
In the formula (A-1-3a-1), p represents an integer of 0 to 5, preferably an integer of 0 to 3, and more preferably an integer of 0 to 2.
When the compound a includes a repeating unit having an acid group, the repeating unit having an acid group is preferably contained in an amount of 80 mol% or less, more preferably 10 to 80 mol% based on the total repeating units of the compound a.
The acid value of the compound A is preferably 20 to 150 mgKOH/g. The upper limit is more preferably 100mgKOH/g or less. The lower limit is preferably not less than 30mgKOH/g, more preferably not less than 35 mgKOH/g. When the acid value of the compound a is within the above range, particularly excellent dispersibility can be easily obtained. Further, excellent developability can be easily obtained.
Compound a may also comprise other repeating units. For example, when the compound A contains a repeating unit represented by the above formula (A-1-2b) as a repeating unit having a graft chain, it may further contain a repeating unit represented by the following formula (A-1-4b) and/or formula (A-1-5 b).
[ chemical formula 18]
Figure BDA0002147187970000231
In the formula (A-1-4b), Rd10And Rd11Each independently represents a hydrogen atom or an alkyl group, and m4 represents an integer of 1 to 5. Rd10And Rd11The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 3.
In the formula (A-1-5b), Re10And Re11Each independently represents a hydrogen atom or an alkyl group, m5 represents an integer of 1 to 5, De1Represents an anionic group, Le1Represents a single bond or a 2-valent linking group, We1The graft chain is shown. Re10And Re11The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 3. As De1Examples of the anionic group include-SO3-、-COO-、-PO4-、-PO4H-, and the like. AsLe1A 2-valent linking group represented bye1Examples of the graft chain include L of the formula (A-1-2)2、W1The graft chain as described in (1).
Specific examples of the compound a include the following.
[ chemical formula 19]
Figure BDA0002147187970000241
[ Table 1]
Figure BDA0002147187970000251
[ Table 2]
Figure BDA0002147187970000261
[ Table 3]
Figure BDA0002147187970000271
[ Table 4]
Figure BDA0002147187970000281
[ Table 5]
Figure BDA0002147187970000291
[ Table 6]
Figure BDA0002147187970000301
[ chemical formula 20]
Figure BDA0002147187970000311
[ Table 7]
Figure BDA0002147187970000321
In the composition of the present invention, the content of the compound a is preferably 5 to 50% by mass based on the total solid content of the composition. The lower limit is preferably 7% by mass or more, and more preferably 10% by mass or more. The upper limit is preferably 40% by mass or less, and more preferably 30% by mass or less.
(polymerizable Compound)
The composition of the present invention may contain a polymerizable compound other than the compound a. The polymerizable compound is preferably a compound capable of polymerizing by the action of a radical. That is, the polymerizable compound is preferably a radical polymerizable compound. The polymerizable compound is preferably a compound having 1 or more ethylenically unsaturated groups, more preferably a compound having 2 or more ethylenically unsaturated groups, and still more preferably a compound having 3 or more ethylenically unsaturated groups. The upper limit of the number of ethylenically unsaturated groups is, for example, preferably 15 or less, more preferably 6 or less. Examples of the ethylenically unsaturated group include a vinyl group, a styryl group, an allyl group, a methallyl group, and a (meth) acryloyl group is preferable. The polymerizable compound is preferably a 3-15 functional (meth) acrylate compound, and more preferably a 3-6 functional (meth) acrylate compound.
The polymerizable compound may be in the form of a monomer or a polymer, and is preferably a monomer. The molecular weight of the polymerizable compound of monomer type is preferably 100 or more and less than 3000. The upper limit is preferably 2000 or less, and more preferably 1500 or less. The lower limit is preferably 150 or more, and more preferably 250 or more. Further, the polymerizable compound is preferably a compound having substantially no molecular weight distribution. The term "substantially free from a molecular weight distribution" means that the compound has a dispersity (weight average molecular weight (Mw)/number average molecular weight (Mn)) of preferably 1.0 to 1.5, more preferably 1.0 to 1.3.
As an example of the polymerizable compound, reference may be made to the descriptions in paragraphs 0033 to 0034 of Japanese patent application laid-open No. 2013-253224, the contents of which are incorporated herein by reference. As the polymerizable compound, preferred are ethyleneoxy-modified pentaerythritol tetraacrylate (commercially available, NK ester ATM-35E; Shin-Nakamura Chemical Co., Ltd., manufactured by Ltd.), dipentaerythritol triacrylate (commercially available, KAYARAD-330; Nippon Kayaku Co., manufactured by Ltd.), dipentaerythritol tetraacrylate (commercially available, KAYARAD-320; Nippon Kayaku Co., manufactured by Ltd.), dipentaerythritol penta (meth) acrylate (as a commercially available product, KAYARAD D-310; manufactured by Nippon Kayaku co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercially available product, KAYARAD DPHA; manufactured by Nippon Kayaku co., Ltd., a-DPH-12E; Shin-Nakamura Chemical co., Ltd.), and compounds having a structure in which the (meth) acryloyl groups thereof are bonded via ethylene glycol residues and/or propylene glycol residues. Also, oligomer types of these can also be used. Further, the contents can be incorporated in the present specification by referring to the descriptions in paragraphs 0034 to 0038 of japanese patent application laid-open No. 2013-253224. Further, polymerizable monomers described in paragraph 0477 of Japanese patent application laid-open No. 2012 and 208494 (paragraph 0585 of the corresponding U.S. patent application publication No. 2012/0235099) and the like can be cited, and these contents are incorporated in the present specification. Further, diglycerin EO (ethylene oxide) -modified (meth) acrylate (commercially available, M-460; TOAGOSEI CO., manufactured by LTD.), pentaerythritol tetraacrylate (Shin-Nakamura Chemical Co., manufactured by Ltd., A-TMMT.), 1, 6-hexanediol diacrylate (Nippon Kayaku Co., manufactured by Ltd., KAYARAD HDDA) are also preferable. Oligomer types of these can also be used. Examples thereof include RP-1040 (manufactured by Nippon Kayaku Co., Ltd.).
The polymerizable compound may have an acid group such as a carboxyl group, a sulfo group, or a phosphoric acid group. Commercially available products of polymerizable compounds having an acid group include ARONIX M-305, M-510, and M-520 (see above: TOAGOSEI CO., LTD.). The acid value of the polymerizable compound having an acid group is preferably 0.1 to 40 mgKOH/g. The lower limit is preferably 5mgKOH/g or more. The upper limit is preferably 30mgKOH/g or less.
It is also a preferable embodiment that the polymerizable compound is a compound having a caprolactone structure. The polymerizable compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule, and examples thereof include an epsilon-caprolactone-modified polyfunctional (meth) acrylate obtained by esterifying a polyhydric alcohol such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerol, diglycerol, and trimethylolmelamine with (meth) acrylic acid and epsilon-caprolactone. As the polymerizable compound having a caprolactone structure, the descriptions in paragraphs 0042 to 0045 of Japanese patent application laid-open No. 2013-253224 can be referred to, and the contents thereof are incorporated in the present specification. Examples of the compound having a caprolactone structure include SR-494 which is a 4-functional acrylate having 4 ethyleneoxy chains manufactured by Sartomer Company, Inc., DPCA-20, DPCA-30, DPCA-60, DPCA-120 and the like commercially available as KAYARAD DPCA series from Nippon Kayaku Co., Ltd., TPA-330 which is a 3-functional acrylate having 3 isobutylene oxy chains, and the like.
As the polymerizable compound, urethane compounds having an ethylene oxide skeleton as described in JP-B-48-041708, JP-A-51-037193, JP-B-2-032293 and JP-B-2-016765, JP-B-58-049860, JP-B-56-017654, JP-B-62-039417 and JP-B-62-039418 are also preferable. Further, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule as described in Japanese patent application laid-open Nos. 63-277653, 63-260909 and 1-105238 can be used. Commercially available urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), and the like.
When the composition of the present invention contains a polymerizable compound other than compound a, the content of the polymerizable compound other than compound a is preferably 0.1 to 40% by mass relative to the total solid content of the composition. The lower limit is, for example, more preferably 0.5% by mass or more, and still more preferably 1% by mass or more. The upper limit is, for example, more preferably 30% by mass or less, and still more preferably 20% by mass or less. The composition of the present invention may not substantially contain a polymerizable compound other than the compound a. The composition of the present invention substantially does not contain a polymerizable compound other than the compound a means that the content of the polymerizable compound other than the compound a is preferably 0.05% by mass or less, more preferably 0.01% by mass or less, and further preferably does not contain it, relative to the total solid content of the composition.
The total content of the compound a and the polymerizable compound other than the compound a is preferably 5 to 50% by mass based on the total solid content of the composition. The lower limit is, for example, more preferably 7% by mass or more, and still more preferably 10% by mass or more. The upper limit is, for example, more preferably 45% by mass or less, and still more preferably 40% by mass or less.
The polymerizable compound may be used alone or in combination of two or more. When two or more polymerizable compounds are used simultaneously, the total amount is preferably within the above range.
[ photopolymerization initiator ]
The composition of the present invention can contain a photopolymerization initiator. The photopolymerization initiator is not particularly limited, and can be appropriately selected from known photopolymerization initiators. For example, a compound having photosensitivity to light in the visible light region from the ultraviolet region is preferable. The photopolymerization initiator is preferably a photo radical polymerization initiator.
Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, and the like), acylphosphine compounds, hexaarylbiimidazole, oxime compounds, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, α -hydroxyketone compounds, α -aminoketone compounds, and the like. From the viewpoint of exposure sensitivity, the photopolymerization initiator is preferably a trihalomethyltriazine compound, a benzyldimethylketal compound, an α -hydroxyketone compound, an α -aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, a cyclopentadiene-benzene-iron complex, a halomethyloxadiazole compound, and a 3-aryl-substituted coumarin compound, more preferably a compound selected from the group consisting of an oxime compound, an α -hydroxyketone compound, an α -aminoketone compound, and an acylphosphine compound, and further preferably an oxime compound. As the photopolymerization initiator, reference is made to the descriptions in paragraphs 0065 to 0111 of Japanese patent application laid-open No. 2014-130173, and the contents thereof are incorporated in the present specification.
Commercially available products of the α -hydroxyketone compound include IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (manufactured by BASF). Commercially available products of the α -aminoketone compound include IRGACURE-907, IRGACURE-369, IRGACURE-379, and IRGACURE-379EG (manufactured by BASF Co., Ltd.). As commercially available acylphosphine compounds, IRGACURE-819 and DAROCUR-TPO (manufactured by BASF) are exemplified.
As the oxime compound, a compound described in Japanese patent laid-open No. 2001-233842, a compound described in Japanese patent laid-open No. 2000-080068, a compound described in Japanese patent laid-open No. 2006-342166, a compound described in Japanese patent laid-open No. 2016-021012, or the like can be used. Examples of oxime compounds which can be preferably used in the present invention include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. Further, there may be mentioned compounds described in J.C.S.Perkin II (1979, pp.1653-1660), J.C.S.Perkin II (1979, pp.156-162), Journal of Photopolymer Science and Technology (Journal of Photopolymer Science and Technology) (1995, pp.202-232), Japanese patent laid-open No. 2000-066385, Japanese patent laid-open No. 2000-080068, Japanese patent laid-open No. 2004-534797, and Japanese patent laid-open No. 2006-342166. As commercially available products, IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, and IRGACURE-OXE04 (manufactured by BASF) can be preferably used. Further, TR-PBG-304 (manufactured by LTD., LTD.), ADEKA ARKLS NCI-831 (manufactured by ADEKA CORPORATION), ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION), and ADEKA OPTMER-N-1919 (the photopolymerization initiator 2 described in the publication of ADEKA CORPORATION, Japanese patent application laid-open No. 2012-014052) can also be used.
In the present invention, an oxime compound having a fluorene ring can also be used as a photopolymerization initiator. Specific examples of oxime compounds having a fluorene ring include compounds described in Japanese patent application laid-open No. 2014-137466. This matter is incorporated in the present specification.
In the present invention, an oxime compound having a fluorine atom can also be used as a photopolymerization initiator. Specific examples of the oxime compound having a fluorine atom include compounds described in Japanese patent application laid-open No. 2010-262028, compounds 24, 36 to 40 described in Japanese patent application laid-open No. 2014-500852, and a compound (C-3) described in Japanese patent application laid-open No. 2013-164471. This matter is incorporated in the present specification.
In the present invention, an oxime compound having a nitro group can be used as a photopolymerization initiator. Oxime compounds having a nitro group are also preferred as dimers. Specific examples of the oxime compound having a nitro group include those described in paragraphs 0031 to 0047 of Japanese patent application laid-open No. 2013-114249, those described in paragraphs 0008 to 0012 and 0070 to 0079 of Japanese patent application laid-open No. 2014-137466, those described in paragraphs 0007 to 0025 of Japanese patent application laid-open No. 4223071, and those described in paragraphs ADEKA ARKLS NCI-831 (manufactured by ADEKA CORPORATION).
Specific examples of oxime compounds preferably used in the present invention will be described below, but the present invention is not limited to these.
[ chemical formula 21]
Figure BDA0002147187970000381
[ chemical formula 22]
Figure BDA0002147187970000391
The oxime compound is preferably a compound having a maximum absorption wavelength in a wavelength region of 350nm to 500nm, and more preferably a compound having a maximum absorption wavelength in a wavelength region of 360nm to 480 nm. Further, the oxime compound is preferably a compound having high absorbance at 365nm and 405 nm.
From the viewpoint of sensitivity, the molar absorption coefficient of the oxime compound at 365nm or 405nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and particularly preferably 5,000 to 200,000.
The molar absorption coefficient of a compound can be measured by a known method. For example, it is preferable to perform the measurement by a spectrophotometer (Cary-5 spectrophotometer, manufactured by Varian corporation) using an ethyl acetate solvent at a concentration of 0.01 g/L.
The photopolymerization initiator also preferably contains an oxime compound and an α -aminoketone compound. By using two of them at the same time, the developability is improved, and a pattern having excellent rectangularity is easily formed. When the oxime compound and the α -aminoketone compound are used together, the α -aminoketone compound is preferably 50 to 600 parts by mass, more preferably 150 to 400 parts by mass, based on 100 parts by mass of the oxime compound.
The content of the photopolymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and still more preferably 1 to 20% by mass, based on the total solid content of the composition. If the content of the photopolymerization initiator is within the above range, the developability is good. The composition of the present invention may contain only one kind of photopolymerization initiator, or may contain two or more kinds. When two or more photopolymerization initiators are contained, the total amount thereof is preferably within the above range.
Resin
The composition of the present invention may contain a resin other than the above-mentioned compound a. Examples of the resin other than the compound a include a resin having no graft chain and a resin having no radical polymerizable unsaturated bond group. In the present invention, the resin is blended for use in, for example, dispersing particles such as a pigment in the composition and for use in a binder. The resin mainly used for dispersing particles such as pigments is called a dispersant. However, these uses of the resin are examples, and the resin may be used for purposes other than these uses.
The weight average molecular weight (Mw) of the resin is preferably 2,000-2,000,000. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less. The lower limit is preferably 3,000 or more, and more preferably 5,000 or more.
Examples of the resin include (meth) acrylic resins, epoxy resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenyl resins, polyarylene ether phosphine oxide resins, polyimide resins, polyamide-imide resins, polyolefin resins, cycloolefin resins, polyester resins, and styrene resins. One of these resins may be used alone, or two or more of them may be used in combination. As the cyclic olefin resin, a norbornene resin can be preferably used from the viewpoint of improvement in heat resistance. Examples of commercially available norbornene resins include ARTON series (for example, ARTON F4520) manufactured by JSR CORPORATION. Examples of the epoxy resin include epoxy resins which are glycidyl etherates of phenol compounds, epoxy resins which are glycidyl etherates of various novolak resins, alicyclic epoxy resins, aliphatic epoxy resins, heterocyclic epoxy resins, glycidyl ester epoxy resins, glycidyl amine epoxy resins, epoxy resins obtained by glycidylating halogenated phenols, condensates of silicon compounds having epoxy groups with silicon compounds other than these, copolymers of polymerizable unsaturated compounds having epoxy groups with other polymerizable unsaturated compounds other than these, and the like. Furthermore, MARPROOF G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (made by NOF CORPORATION, epoxy group-containing polymer), and the like can also be used. Further, as the resin, the resin described in examples of International publication WO2016/088645 can be used.
The resin used in the present invention may have an acid group. Examples of the acid group include a carboxyl group, a phosphoric group, a sulfo group, a phenolic hydroxyl group, and the like, and a carboxyl group is preferable. These acid groups may be only one kind or two or more kinds. Resins having acid groups can also be used as alkali-soluble resins.
The resin having an acid group is preferably a polymer having a carboxyl group in a side chain. Specific examples thereof include alkali-soluble phenolic resins such as methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, and novolak resins, acidic cellulose derivatives having a carboxyl group in a side chain, and resins obtained by adding an acid anhydride to a polymer having a hydroxyl group. In particular, as the alkali-soluble resin, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is preferable. Examples of the other monomer copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. Examples of the alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like, and examples of the vinyl compound, examples thereof include styrene, α -methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer and polymethyl methacrylate macromonomer. Further, as the other monomer, an N-substituted maleimide monomer described in Japanese patent application laid-open No. 10-300922, for example, N-phenylmaleimide, N-cyclohexylmaleimide, and the like can be used. The other monomer copolymerizable with these (meth) acrylic acids may be only one kind or two or more kinds.
The resin having an acid group may further have a polymerizable group. Examples of the polymerizable group include allyl group, methallyl group, and (meth) acryloyl group. Commercially available products include DIANAL NR series (manufactured by Mitsubishi Chemical corporation), Photomer6173 (urethane acrylate oligomer having a carboxyl group, Diamond Shamrock Co., manufactured by Ltd.), VISCOAT R-264, KS RESIST 106 (manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.), CYCLOMER P series (for example, ACA230AA), PLACCEL CF200 series (manufactured by Daicel corporation), Ebecryl3800 (manufactured by Daicel UCB Co., Ltd.), AKURIKYUA RD-F8(NIPPON SHOKUBA CO., manufactured by LTD.), and the like.
The resin having an acid group can preferably use a benzyl (meth) acrylate/(meth) acrylic acid copolymer, a benzyl (meth) acrylate/(meth) acrylic acid 2-hydroxyethyl ester copolymer, a multi-component copolymer composed of benzyl (meth) acrylate/(meth) acrylic acid/other monomer. Further, it is also possible to preferably use a resin obtained by copolymerizing 2-hydroxyethyl (meth) acrylate, a 2-hydroxypropyl (meth) acrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, a 2-hydroxy-3-phenoxypropyl acrylate/polymethyl methacrylate macromonomer/benzyl methacrylate/methacrylic acid copolymer described in Japanese unexamined patent publication No. 7-140654, 2-hydroxyethyl methacrylate/polystyrene macromonomer/methyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, and the like.
The resin having an acid group is preferably a polymer containing a repeating unit derived from a monomer component containing a compound represented by the following formula (ED1) and/or a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as "ether dimer").
[ chemical formula 23]
Figure BDA0002147187970000421
In the formula (ED1), R1And R2Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
[ chemical formula 24]
Figure BDA0002147187970000422
In the formula (ED2), R represents a hydrogen atom or an organic group having 1-30 carbon atoms. As a specific example of the formula (ED2), reference can be made to the description of Japanese patent laid-open No. 2010-168539.
As a specific example of the ether dimer, for example, refer to paragraph 0317 of Japanese patent application laid-open No. 2013-029760, which is incorporated herein by reference. The ether dimer may be only one kind or two or more kinds.
The resin having an acid group may include a repeating unit derived from a compound represented by the following formula (X).
[ chemical formula 25]
Figure BDA0002147187970000431
In the formula (X), R1Represents a hydrogen atom or a methyl group, R2Represents an alkylene group having 2 to 10 carbon atoms, R3Represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may contain a benzene ring. n represents an integer of 1 to 15.
With respect to the resin having an acid group, reference can be made to the descriptions in paragraphs 0558 to 0571 of Japanese patent application laid-open No. 2012 and 208494 (corresponding to paragraphs 0685 to 0700 of U.S. patent application publication No. 2012/0235099), and the descriptions in paragraphs 0076 to 0099 of Japanese patent application laid-open No. 2012 and 198408, and these contents are incorporated in the present specification. Further, commercially available resins having an acid group can also be used. For example, Acrybase FF-426 (manufactured by FUJIKURA KASEI CO., LTD.) and the like can be given.
The acid value of the resin having an acid group is preferably 30 to 200 mgKOH/g. The lower limit is preferably 50mgKOH/g or more, more preferably 70mgKOH/g or more. The upper limit is preferably not more than 150mgKOH/g, more preferably not more than 120 mgKOH/g.
Examples of the resin having an acid group include resins having the following structures. In the following structural formula, Me represents a methyl group.
[ chemical formula 26]
Figure BDA0002147187970000441
The composition of the present invention can also contain a resin as a dispersant. Examples of the dispersant include an acidic dispersant (acidic resin) and a basic dispersant (basic resin). Here, the acidic dispersant (acidic resin) means a resin having an acid group in an amount larger than that of a base group. The acidic dispersant (acidic resin) is preferably a resin in which the amount of the acid group is 70 mol% or more, and more preferably a resin substantially including only the acid group, when the total amount of the acid group and the amount of the base group is 100 mol%. The acid group of the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 40 to 105mgKOH/g, more preferably 50 to 105mgKOH/g, and still more preferably 60 to 105 mgKOH/g. The basic dispersant (basic resin) is a resin having a larger amount of basic groups than that of acid groups. The basic dispersant (basic resin) is preferably a resin having a base content of more than 50 mol% when the total amount of the acid groups and the base content is 100 mol%. The basic group of the basic dispersant is preferably an amino group.
The resin used as the dispersant preferably contains a repeating unit having an acid group. The resin used as the dispersant contains a repeating unit having an acid group, so that when a pattern is formed by photolithography, residue generated on the substrate of the pixel can be further reduced.
The resin used as the dispersant is preferably a graft copolymer. The graft copolymer has affinity with a solvent due to the graft chain, and therefore, the pigment dispersibility and the dispersion stability with time are excellent. The details of the graft copolymer can be found in paragraphs 0025 to 0094 of Japanese patent application laid-open No. 2012 and 255128, which is incorporated herein by reference. Specific examples of the graft copolymer include the following resins. The following resins are also resins having an acid group (alkali-soluble resins). The graft copolymer includes resins described in paragraphs 0072 to 0094 of Japanese patent application laid-open No. 2012 and 255128, the contents of which are incorporated herein by reference.
[ chemical formula 27]
Figure BDA0002147187970000451
In the present invention, as the resin (dispersant), an oligoimine dispersant containing a nitrogen atom in at least 1 position of the main chain and the side chain is preferably used. The oligo-imine dispersant preferably includes a resin having a basic nitrogen atom in at least one of a main chain and a side chain, the structural unit including a partial structure X having a functional group with a pKa14 or less, and the side chain including a side chain Y having 40 to 10,000 atoms. The basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom. Regarding the oligoimine dispersant, reference is made to the descriptions in paragraphs 0102 to 0166 of Japanese patent application laid-open No. 2012 and 255128, the contents of which are incorporated herein by reference. The oligomeric imine-based dispersant can be a resin described in paragraphs 0168 to 0174 of Japanese patent application laid-open No. 2012 and 255128.
The dispersant is available as a commercially available product, and specific examples thereof include Disperbyk-111(BYK Chemie), SOLSPERSE 76500(Lubrizol Japan Ltd.). Further, the pigment dispersant described in paragraphs 0041 to 0130 of Japanese patent application laid-open No. 2014-130338 can be used and incorporated in the present specification. Further, a resin having the above acid group or the like can be used as the dispersant.
When the composition of the present invention contains a resin, the content of the resin is preferably more than 0 mass% and 30 mass% or less with respect to the total solid content of the composition of the present invention.
Color material for transmitting infrared ray and shielding visible light
The composition of the present invention may contain a color material that transmits infrared light and blocks visible light (hereinafter, also referred to as a visible light blocking color material). In the present invention, the color material for shielding visible light is preferably a color material that absorbs light in the violet to red wavelength region. In the present invention, the color material for shielding visible light is preferably a color material for shielding light having a wavelength region of 400 to 640 nm. The color material for shielding visible light is preferably a color material that transmits light having a wavelength of 900 to 1300 nm. In the present invention, the color material for shielding visible light preferably satisfies at least 1 of the following requirements (a) and (B).
(1): two or more color colorants are contained, and black is formed by a combination of the two or more color colorants.
(2): contains an organic black colorant. (2) In the embodiment (1), a color colorant is preferably contained.
In the present invention, the colored colorant means a colorant other than a white colorant and a black colorant. In the present invention, the organic black colorant as a color material for shielding visible light is a material that absorbs visible light but transmits at least a part of infrared rays. Accordingly, in the present invention, the organic black colorant as the color material for shielding visible light does not include a black colorant that absorbs both visible light and infrared light, for example, carbon black or titanium black. The organic black colorant is preferably a colorant having an absorption maximum wavelength in a wavelength range of 400nm to 700 nm.
In the present invention, for example, the ratio A/B of the minimum value A of absorbance in the wavelength range of 400 to 640nm to the minimum value B of absorbance in the wavelength range of 900 to 1300nm is preferably 4.5 or more with respect to the color material for shielding visible light.
The above properties can be satisfied by one kind of raw material, or by a combination of a plurality of kinds of raw materials. For example, in the case of the embodiment (1), it is preferable to combine a plurality of color colorants to satisfy the spectral characteristics. In the case of the embodiment (2), the spectral characteristics may be satisfied by an organic black colorant. The spectral characteristics may be satisfied by a combination of an organic black colorant and a color colorant.
(color colorant)
In the present invention, the chromatic colorant is preferably a colorant selected from the group consisting of a red colorant, a green colorant, a blue colorant, a yellow colorant, a violet colorant, and an orange colorant. In the present invention, the color colorant may be a pigment or a dye. Pigments are preferred. As for the pigment, the average particle diameter (r) is preferably 20 nm. ltoreq. r.ltoreq.300 nm, more preferably 25 nm. ltoreq. r.ltoreq.250 nm, and further preferably 30 nm. ltoreq. r.ltoreq.200 nm. The "average particle diameter" herein refers to an average particle diameter of secondary particles of the primary particles in which the pigments are aggregated. In the particle size distribution of the secondary particles of the pigment to be used (hereinafter, simply referred to as "particle size distribution"), the secondary particles contained in the range of the average particle size ± 100nm are preferably 70 mass% or more, more preferably 80 mass% or more of the whole. The particle size distribution of the secondary particles can be measured using a scattering intensity distribution.
The pigment is preferably an organic pigment. Examples of the organic pigment include the following.
Color index (c.i.) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35:1, 36:1, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 182, 177, 187, 185, 193, 185, 194, 199, and the like (e.g. the above pigments are Yellow pigments);
pigment Orange 2, 5, 13, 16, 17:1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. (above, Orange pigments);
c.i. pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279, etc. (Red pigments above);
pigment Green 7, 10, 36, 37, 58, 59, etc. (above, Green pigments);
pigment Violet 1, 19, 23, 27, 32, 37, 42, etc. (above, Violet pigments);
pigment Blue 1, 2, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64, 66, 79, 80, etc. (above, Blue pigment);
these organic pigments can be used alone or in combination of plural kinds.
The dye is not particularly limited, and a known dye can be used. As the chemical structure, dyes of pyrazole azo series, aniline azo series, triarylmethane series, anthraquinone series, anthrapyridone series, benzylidene series, oxonol series, pyrazolotriazole azo series, pyridone azo series, cyanine series, phenothiazine series, pyrrolopyrazole azomethine series, xanthene series, phthalocyanine series, benzopyran series, indigo series, pyrromethene series, and the like can be used. Also, multimers of these dyes can be used. Further, dyes described in Japanese patent laid-open Nos. 2015-028144 and 2015-034966 may be used.
The color material for shielding visible light preferably contains two or more selected from a red colorant, a blue colorant, a yellow colorant, a violet colorant, and a green colorant. That is, the color material for shielding visible light is preferably formed into black by combining two or more colorants selected from a red colorant, a blue colorant, a yellow colorant, a violet colorant, and a green colorant. Preferred combinations include the following.
(1) A red colorant and a blue colorant.
(2) A red colorant, a blue colorant and a yellow colorant.
(3) A red colorant, a blue colorant, a yellow colorant and a violet colorant.
(4) A red colorant, a blue colorant, a yellow colorant, a violet colorant and a green colorant.
(5) A red colorant, a blue colorant, a yellow colorant and a green colorant.
(6) A mode containing a red colorant, a blue colorant and a green colorant.
(7) A mode containing a yellow colorant and a violet colorant.
In the embodiment (1), the mass ratio of the red colorant to the blue colorant is preferably 20 to 80:20 to 80, more preferably 20 to 60:40 to 80, and still more preferably 20 to 50:50 to 80.
In the aspect (2), the mass ratio of the red colorant, the blue colorant and the yellow colorant is preferably 10 to 80:20 to 80:10 to 40, more preferably 10 to 60:30 to 80:10 to 30, and still more preferably 10 to 40:40 to 80:10 to 20.
In the aspect (3), the mass ratio of the red colorant, the blue colorant, the yellow colorant and the violet colorant is preferably 10 to 80:20 to 80:5 to 40, more preferably 10 to 60:30 to 80:5 to 30, and still more preferably 10 to 40:40 to 80:5 to 20.
In the aspect (4), the mass ratio of the red colorant, the blue colorant, the yellow colorant, the violet colorant, and the green colorant is preferably 10 to 80:20 to 80:5 to 40, more preferably 10 to 60:30 to 80:5 to 30, and even more preferably 10 to 40:40 to 80:5 to 20.
In the aspect (5), the mass ratio of the red colorant, the blue colorant, the yellow colorant and the green colorant is preferably 10 to 80:20 to 80:5 to 40, more preferably 10 to 60:30 to 80:5 to 30, and still more preferably 10 to 40:40 to 80:5 to 20.
In the aspect (6), the mass ratio of the red colorant to the blue colorant to the green colorant is preferably 10 to 80:20 to 80:10 to 40, more preferably 10 to 60:30 to 80:10 to 30, and still more preferably 10 to 40:40 to 80:10 to 20.
In the aspect (7), the mass ratio of the yellow colorant to the violet colorant is preferably 10 to 50:40 to 80, more preferably 20 to 40:50 to 70, and still more preferably 30 to 40:60 to 70.
The Yellow colorant is preferably c.i. pigment Yellow 139, 150, 185, more preferably c.i. pigment Yellow 139, 150, and still more preferably c.i. pigment Yellow 139. As the Blue colorant, c.i. pigment Blue 15:6 is preferable. As the Violet colorant, c.i. pigment Violet 23 is preferable. As the Red colorant, c.i. pigment Red 122, 177, 224, 254 is preferable, c.i. pigment Red 122, 177, 254 is more preferable, and c.i. pigment Red 254 is further preferable. As the Green colorant, c.i. pigment Green 7, 36, 58, 59 is preferable.
(organic Black colorant)
In the present invention, examples of the organic black coloring agent include a dibenzofuranone compound, a azomethine compound, a perylene compound, and an azo compound, and the dibenzofuranone compound and the perylene compound are preferable. Examples of the dibenzofuranone compound include those described in Japanese Kokai publication No. 2010-534726, Japanese Kokai publication No. 2012-515233, and Japanese Kokai publication No. 2012-515234, and can be obtained as Irgaphor Black, manufactured by BASF corporation, for example. Examples of the perylene compound include c.i. pigment Black 31 and 32. As the azomethine compound, there are mentioned Japanese patent application laid-open Nos. H1-170601 and H2-034664, and the azomethine compound is available as "phthalocyanine Black A1103" manufactured by Dainiciseika Color & Chemicals Mfg. Co., Ltd.
In the present invention, the dibenzofuranone compound is preferably a compound represented by the following formula or a mixture thereof.
[ chemical formula 28]
Figure BDA0002147187970000501
In the formula, R1And R2Each independently represents a hydrogen atom or a substituent, R3And R4Each independently represents a substituent, a and b each independently represents an integer of 0 to 4, and when a is 2 or more, a plurality of R' s3May be the same or different, and a plurality of R' s3Can be bonded to form a ring, and when b is 2 or more, a plurality of R4May be the same or different, and a plurality of R' s4May be bonded to form a ring.
R1～R4The substituents are halogen atoms, cyano groups, nitro groups, alkyl groups, alkenyl groups, alkynyl groups, aralkyl groups, aryl groups, heteroaryl groups, -OR301、-COR302、-COOR303、-OCOR304、-NR305R306、-NHCOR307、-CONR308R309、-NHCONR310R311、-NHCOOR312、-SR313、-SO2R314、-SO2OR315、-NHSO2R316or-SO2NR317R318，R301～R318Each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group.
The details of the dibenzofuranone compound can be found in paragraphs 0014 to 0037 of Japanese patent application publication No. 2010-534726, which is incorporated herein by reference.
In the present invention, when an organic black colorant is used as a color material for shielding visible light, it is preferably used in combination with a color colorant. By using both an organic black colorant and a color colorant, excellent spectral characteristics can be easily obtained. Examples of the color colorant used in combination with the organic black colorant include a red colorant, a blue colorant, and a violet colorant, and the red colorant and the blue colorant are preferable. These may be used alone or in combination of two or more.
The mixing ratio of the color colorant and the organic black colorant is preferably 10 to 200 parts by mass, more preferably 15 to 150 parts by mass, based on 100 parts by mass of the organic black colorant.
In the present invention, the content of the pigment in the visible light shielding color material is preferably 95% by mass or more, more preferably 97% by mass or more, and still more preferably 99% by mass or more, based on the total amount of the visible light shielding color material.
In the composition of the present invention, the content of the color material for shielding visible light is preferably 10 to 60% by mass based on the total solid content of the composition. The upper limit is preferably 50% by mass or less, more preferably 45% by mass or less. The lower limit is preferably 20% by mass or more, and more preferably 25% by mass or more.
Pigment derivatives
The composition of the invention can also contain pigment derivatives. The pigment derivative may have a structure in which a part of the pigment is substituted with an acid group, a base group, a group having a salt structure, or a phthalimide methyl group. As the pigment derivative, a compound represented by formula (B1) is preferred.
[ chemical formula 29]
Figure BDA0002147187970000511
In the formula (B1), P represents a dye structure, L represents a single bond or a linking group, X represents an acid group, a base group, a group having a salt structure, or a phthalimidomethyl group, m represents an integer of 1 or more, n represents an integer of 1 or more, when m is 2 or more, a plurality of L and X may be different from each other, and when n is 2 or more, a plurality of X may be different from each other.
In the formula (B1), P represents a pigment structure, and is preferably at least one selected from the group consisting of a pyrrolopyrrole pigment structure, a diketopyrrolopyrrole pigment structure, a quinacridone pigment structure, an anthraquinone pigment structure, a dianthraquinone pigment structure, a benzindole pigment structure, a thiazininoindole pigment structure, an azo pigment structure, a quinophthalone pigment structure, a phthalocyanine pigment structure, a naphthalocyanine pigment structure, a dioxazine pigment structure, a perylene pigment structure, a perinone pigment structure, a benzimidazolone pigment structure, a benzothiazole pigment structure, a benzimidazole pigment structure, and a benzoxazole pigment structure, more preferably at least one selected from the group consisting of a pyrrolopyrrole pigment structure, a diketopyrrolopyrrole pigment structure, a quinacridone pigment structure, and a benzimidazolone pigment structure, and particularly preferably a pyrrolopyrrole pigment structure.
In the formula (B1), L represents a single bond or a linking group. The linking group is preferably a group consisting of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms and 0 to 20 sulfur atoms, and may be unsubstituted or substituted.
In the formula (B1), X represents an acid group, a base group, a group having a salt structure, or a phthalimide methyl group, and preferably an acid group or a base group. Examples of the acid group include a carboxyl group and a sulfo group. Examples of the base include an amino group.
Examples of the pigment derivative include compounds having the following structures. Further, compounds described in jp 56-118462 a, jp 63-264674 a, jp 1-217077 a, jp 3-009961 a, jp 3-026767 a, jp 3-153780 a, jp 3-045662 a, jp 4-285669 a, jp 6-145546 a, jp 6-212088 a, jp 6-240158 a, jp 10-030063 a, jp 10-195326 a, paragraphs 0086 to 0098 of international publication WO2011/024896 a, paragraphs 0063 to 0094 of international publication WO2012/102399 and the like can be used, and the contents thereof can be incorporated in the present specification.
[ chemical formula 30]
Figure BDA0002147187970000531
When the composition of the present invention contains a pigment derivative, the content of the pigment derivative is preferably 1 to 50 parts by mass per 100 parts by mass of the pigment. The lower limit is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more. The upper limit is preferably 40 parts by mass or less, and more preferably 30 parts by mass or less. When the content of the pigment derivative is within the above range, the dispersibility of the pigment is improved and the aggregation of the pigment can be effectively suppressed. The pigment derivative may be used alone or in combination of two or more. When two or more kinds are used, the total amount is preferably in the above range.
Solvent
The compositions of the present invention can contain a solvent. Examples of the solvent include organic solvents. The solvent is not particularly limited as long as it satisfies the solubility of each component or the coatability of the composition. Examples of the organic solvent include esters, ethers, ketones, and aromatic hydrocarbons. For details of these, reference can be made to paragraph 0223 of International publication WO2015/166779, which is incorporated herein by reference. Also, ester solvents in which a cyclic alkyl group is substituted and ketone solvents in which a cyclic alkyl group is substituted can be preferably used. Specific examples of the organic solvent include methylene chloride, methyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diglyme, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate. In the present invention, one kind of the organic solvent may be used alone, or two or more kinds may be used in combination. However, aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as a solvent may be reduced to be preferable for environmental reasons, etc. (for example, 50 mass ppm (parts per million) or less, or 10 mass ppm or less, or 1 mass ppm or less may be set with respect to the total amount of organic solvents).
In the present invention, a solvent having a small metal content is preferably used, and the metal content of the solvent is preferably 10 parts per billion (ppb) or less by mass, for example. Quality ppt (parts per trillion) grades of solvents, such as those provided by Toyo Gosei co., Ltd (journal of chemical industry, 2015, 11/13/d), may be used as desired.
Examples of a method for removing impurities such as metals from a solvent include distillation (molecular distillation, membrane distillation, or the like) and filtration using a filter. The pore diameter of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and still more preferably 3 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.
The solvent may contain isomers (compounds having the same atomic number but different structures). The isomer may include only one kind or a plurality of kinds.
In the present invention, the organic solvent preferably has a peroxide content of 0.8mmol/L or less, and more preferably contains substantially no peroxide.
The content of the solvent is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and still more preferably 25 to 75% by mass, based on the total amount of the composition.
Polymerization inhibitor
The compositions of the present invention can contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, gallic acid phenol (pyrogallol), t-butyl catechol, benzoquinone, 4 '-thiobis (3-methyl-6-t-butylphenol), 2' -methylenebis (4-methyl-6-t-butylphenol), and N-nitrosophenylhydroxylamine salt (ammonium salt, cerium salt, and the like). Among them, p-methoxyphenol is preferable. The content of the polymerization inhibitor is preferably 0.001 to 5% by mass based on the total solid content of the composition.
Silane coupling agent
The composition of the present invention can contain a silane coupling agent. In the present invention, the silane coupling agent refers to a silane compound having a hydrolyzable group and a functional group other than the hydrolyzable group. The hydrolyzable group is a substituent that is directly bonded to a silicon atom and further generates a siloxane bond by at least one of a hydrolysis reaction and a fusion reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, and an acyloxy group, with an alkoxy group being preferred. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Examples of the functional group other than the hydrolyzable group include a vinyl group, a styryl group, a (meth) acryloyl group, a mercapto group, an epoxy group, an oxetanyl group, an amino group, a ureido group, a thioether group, an isocyanate group, and a phenyl group, and a (meth) acryloyl group and an epoxy group are preferable. Examples of the silane coupling agent include compounds described in paragraphs 0018 to 0036 of Japanese patent application laid-open No. 2009-288703 and compounds described in paragraphs 0056 to 0066 of Japanese patent application laid-open No. 2009-242604, which are incorporated herein by reference.
The content of the silane coupling agent is preferably 0.01 to 15.0% by mass, more preferably 0.05 to 10.0% by mass, based on the total solid content of the composition. The silane coupling agent may be one kind only, or two or more kinds. When the number is two or more, the total amount is preferably in the above range.
Surface active agent
The compositions of the present invention may contain a surfactant. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. The surfactant can be referred to paragraphs 0238 to 0245 of International publication WO2015/166779, which is incorporated herein by reference.
In the present invention, the surfactant is preferably a fluorine-based surfactant. The liquid characteristics (particularly, fluidity) of the composition of the present invention can be further improved by including the fluorine-based surfactant, and the liquid saving properties can be further improved. Further, a film with less thickness variation can be formed.
The fluorine content in the fluorine-containing surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. In view of uniformity of the thickness of the coating film and liquid saving properties, a fluorine-based surfactant having a fluorine content within the above range is effective and has good solubility in the composition.
Specific examples of the fluorine-based surfactant include surfactants described in paragraphs 0060 to 0064 of Japanese patent application laid-open No. 2014-041318 (paragraphs 0060 to 0064 of corresponding International patent application laid-open No. 2014/017669), and surfactants described in paragraphs 0117 to 0132 of Japanese patent application laid-open No. 2011-132503, and these are incorporated herein. Commercially available fluorine-based surfactants include MEGAFACE F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780 (manufactured by DIC Corporation, supra), Fluorad FC430, FC431, FC171 (manufactured by Sumitomo 3M Limited, supra), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (manufactured by ASAHI GLASS CO., LTD., supra), PolyFox 636, PF656, PF6320, PF6520, and PF7002 (manufactured by OMNOVA Solutions Inc., supra).
Further, the fluorine-based surfactant can preferably use an acrylic compound having a molecular structure of a functional group containing a fluorine atom, and when heated, a part of the functional group containing a fluorine atom is cleaved and the fluorine atom is volatilized. Examples of the fluorine-based surfactant include MEGAFACE DS series (chemical industry journal, 2016, 2, 22 days) (sunrise industry news, 2016, 2, 23 days), manufactured by DIC Corporation, for example, MEGAFACE DS-21.
The fluorine-based surfactant may be a block polymer. Examples thereof include compounds described in Japanese patent application laid-open No. 2011-089090. The fluorine-based surfactant can also preferably use a fluorine-containing polymer compound containing a repeating unit derived from a (meth) acrylate compound having a fluorine atom and a repeating unit derived from a (meth) acrylate compound having 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups). The following compounds are also exemplified as the fluorine-based surfactant used in the present invention.
[ chemical formula 31]
Figure BDA0002147187970000571
The weight average molecular weight of the compound is preferably 3,000 to 50,000, for example, 14,000. In the above compounds,% representing the proportion of the repeating unit is mass%.
Further, as the fluorine-containing surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in a side chain can be used. Specific examples thereof include compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of Japanese patent application laid-open No. 2010-164965, for example, MEGAFACE RS-101, MAGAFACE RS-102, MEGAFACE RS-718K and MEGAFACE RS-72-K manufactured by DIC Corporation. As the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of Japanese patent laid-open publication No. 2015-117327 can be used.
Examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (e.g., glycerol propoxylate, glycerol ethoxylate), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF Co., Ltd.), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF Co., Ltd.), SOLSPERSE 20000 (manufactured by Lubrizol Japan Limited), NCW-101, NCW-1001, NCW-1002(Wako Pure Industries, Ltd.), PIONIN D-6112, D-6112-6332-W, D-tamol & 3915 (Tamoto 3915, Co., Ltd., Co., Ltd., Japan Chemical Co., Ltd., Japan, Tab., ltd), OLFIN E1010, Surfynol 104, 400, 440(Nissin Chemical co., ltd), and the like.
The content of the surfactant is preferably 0.001 to 5.0% by mass, more preferably 0.005 to 3.0% by mass, based on the total solid content of the composition of the present invention. The surfactant may be one kind only, or two or more kinds. When the number is two or more, the total amount is preferably in the above range.
Ultraviolet absorbent
The composition of the present invention can contain an ultraviolet absorber. As the ultraviolet absorber, a conjugated diene compound, an aminobutadiene compound, a methylbenzoyl compound, a coumarin compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, and the like can be used. The details of these can be found in paragraphs 0052 to 0072 of jp 2012-208374 and paragraphs 0317 to 0334 of jp 2013-068814, which are incorporated herein by reference. Examples of commercially available products of the conjugated diene compound include UV-503 (manufactured by DAITO CHEMICAL co., ltd). As the benzotriazole compound, MIYOSHI OIL & FAT co, MYUA series manufactured by ltd (journal of chemical industry, 2016, 2 months, 1 days). The ultraviolet absorber is preferably a compound represented by any one of the formulae (UV-1) to (UV-3), more preferably a compound represented by the formula (UV-1) or (UV-3), and still more preferably a compound represented by the formula (UV-1).
[ chemical formula 32]
Figure BDA0002147187970000581
In the formula (UV-1), R101And R102Each independently represents a substituent, and m1 and m2 each independently represents 0 to 4.
In the formula (UV-2), R201And R202Each independently represents a hydrogen atom or an alkyl group, R203And R204Each independently represents a substituent.
In the formula (UV-3), R301～R303Each independently represents a hydrogen atom or an alkyl group, R304And R305Each independently represents a substituent.
Specific examples of the compounds represented by the formulae (UV-1) to (UV-3) include the following compounds.
[ chemical formula 33]
Figure BDA0002147187970000591
In the composition of the present invention, the content of the ultraviolet absorber is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, based on the total solid content of the composition. In the present invention, only one kind of the ultraviolet absorber may be used, or two or more kinds thereof may be used. When two or more kinds are used, the total amount is preferably in the above range.
[ antioxidant ]
The compositions of the present invention can contain an antioxidant. Examples of the antioxidant include phenol compounds, phosphite compounds, and thioether compounds. As the phenol compound, any phenol compound known as a phenol antioxidant can be used. Preferable examples of the phenol compound include hindered phenol compounds. Preferred are compounds having a substituent at a site (ortho position) adjacent to the phenolic hydroxyl group. The substituent is preferably a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms. Further, the antioxidant is preferably a compound having a phenol group and a phosphite group in the same molecule. Further, as the antioxidant, a phosphorus-based antioxidant can also be preferably used. Examples of the phosphorus-based antioxidant include tris [2- [ [2,4,8, 10-tetrakis (1, 1-dimethylethyl) dibenzo [ d, f ] [1,3,2] dioxaphosphorin cycloheptan-6-yl ] oxy ] ethyl ] amine, tris [2- [ (4,6,9, 11-tetra-tert-butyldibenzo [ d, f ] [1,3,2] dioxaphosphorin cycloheptan-2-yl) oxy ] ethyl ] amine, and phosphite ethyl bis (2, 4-di-tert-butyl-6-methylphenyl). Examples of commercially available antioxidants include ADKSTAAO-20, ADKSTAAO-30, ADKSTATAAO-40, ADKSTAAO-50F, ADKSTAAO-60G, ADKSTAAO-80, and ADKSTAAO-330 (manufactured by ADEKA CORPORATION).
In the composition of the present invention, the content of the antioxidant is preferably 0.01 to 20% by mass, more preferably 0.3 to 15% by mass, based on the total solid content of the composition. The antioxidant may be used alone or in combination of two or more. When two or more kinds are used, the total amount is preferably in the above range.
Other components
The curable composition of the present invention may contain, as necessary, a sensitizer, a curing accelerator, a filler, a thermosetting accelerator, a plasticizer, and other auxiliaries (for example, conductive particles, a filler, a defoaming agent, a flame retardant, a leveling agent, a peeling accelerator, a fragrance, a surface tension adjusting agent, a chain transfer agent, and the like). By appropriately containing these components, properties such as film physical properties can be adjusted. For these components, for example, reference can be made to the descriptions in paragraphs 0183 of Japanese patent application laid-open No. 2012 and 003225 (0237 of the corresponding specification of U.S. patent application publication No. 2013/0034812), paragraphs 0101 to 0104 and paragraphs 0107 to 0109 of Japanese patent application laid-open No. 2008 and 250074, and the contents thereof are incorporated into the present specification.
The viscosity (23 ℃) of the composition of the present invention is preferably in the range of 1 to 100 mPas when a film is formed by coating, for example. The lower limit is more preferably 2 mPas or more, and still more preferably 3 mPas or more. The upper limit is preferably 50 mPas or less, more preferably 30 mPas or less, particularly preferably 15 mPas or less.
The container for the composition of the present invention is not particularly limited, and a known container can be used. Further, for the purpose of suppressing the contamination of impurities into the raw material or the composition, it is preferable to use a multilayer bottle having an inner wall of the container made of 6 kinds of 6-layer resins or a bottle having a 7-layer structure made of 6 kinds of resins. Examples of such containers include those described in Japanese patent laid-open publication No. 2015-123351.
The use of the composition of the present invention is not particularly limited. For example, the present invention can be preferably used for forming a near infrared ray cut filter or the like. Further, the composition of the present invention may further contain a color material for shielding visible light, thereby forming an infrared transmission filter which transmits only near infrared rays having a specific wavelength or longer.
< preparation method of composition >
The composition of the present invention can be prepared by mixing the aforementioned ingredients. For example, when a composition is prepared, the composition can be prepared by dissolving or dispersing all the components in a solvent at the same time, or if necessary, a solution or dispersion of 2 or more components appropriately blended with each component can be prepared in advance, and these can be mixed at the time of use (at the time of coating) to prepare a composition.
When the composition of the present invention contains particles such as pigments, it is preferable to include a process for dispersing the particles. In the process of dispersing the particles, examples of the mechanical force used for dispersing the particles include compression, extrusion, impact, shearing, pitting and the like. Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint mixers, microfluidizers, high-speed impellers, sand mills, jet mixers, high-pressure wet atomization, ultrasonic dispersion, and the like. In addition, in the pulverization of particles in a sand mill (bead mill), it is preferable to perform the treatment under the condition that the pulverization efficiency is improved by using microbeads having a small diameter and increasing the packing ratio of the microbeads. Further, it is preferable to remove coarse particles by filtration, centrifugation, or the like after the pulverization treatment. Further, the process and the dispersing machine for dispersing the particles can preferably use the process and the dispersing machine described in "the entire dispersion technology, johaokiko co., ltd. release, 7/15/2005" and "the actual comprehensive data set of dispersion technology and industrial application centered on suspension (solid/liquid dispersion system), release of the department of business development center, 10/1978", and paragraph 0022 of japanese patent application laid-open No. 2015-157893. In the process of dispersing the particles, the particle size reduction treatment can be performed in a polishing step. For example, the materials, equipment, and processing conditions used in the polishing step can be described in Japanese patent laid-open Nos. 2015-194521 and 2012-046629.
When the composition is prepared, it is preferable to filter the composition using a filter for the purpose of removing impurities or reducing defects. The filter may be used without particular limitation as long as it is conventionally used for filtration applications and the like. Examples of the filter include filters using a fluororesin such as Polytetrafluoroethylene (PTFE), a polyamide resin such as nylon (e.g., nylon-6, 6), a polyolefin resin (including a high-density, ultrahigh-molecular-weight polyolefin resin) such as polyethylene or polypropylene (PP), and the like. Among these materials, polypropylene (containing high-density polypropylene) and nylon are preferable.
The pore diameter of the filter is preferably about 0.01 to 7.0 μm, more preferably about 0.01 to 3.0 μm, and most preferably about 0.05 to 0.5 μm. When the pore diameter of the filter is within the above range, fine foreign matter can be reliably removed. Further, a fibrous filter is also preferably used. Examples of the fibrous filter medium include polypropylene fibers, nylon fibers, and glass fibers. Specifically, there may be mentioned filter elements of the ROKI techon co., ltd, SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.), and SHPX type series (SHPX003, etc.).
When filters are used, different filters (e.g., a1 st filter and a2 nd filter, etc.) may be combined. In this case, the filtration by each filter may be performed only once, or may be performed twice or more.
Further, filters having different pore diameters within the above range may be combined. The pore size here can be referred to the filter manufacturer's nominal value. Commercially available FILTERs can be selected from various FILTERs provided by NIHON PALL ltd. (DFA4201NIEY, etc.), Advantec Toyo Kaisha, ltd., NIHON Entegris K.K, (formerly Japan MICRO co., LTD.), kit MICRO FILTER CORPORATION, etc., for example.
The 2 nd filter can be made of the same material as the 1 st filter.
The filtration using the 1 st filter may be performed only on the dispersion liquid, or may be performed using the 2 nd filter after mixing other components.
< membrane >
Next, the film of the present invention will be explained. The film of the present invention is obtained from the above-described composition of the present invention. The film of the present invention can be preferably used as a near infrared ray cut filter or an infrared ray transmission filter. And, it can also be used as a heat ray shielding filter. The film of the present invention may have a pattern or may be a film having no pattern (flat film). The film of the present invention may be used by being laminated on a support, or may be used after being peeled off from a support. When the film of the present invention is used as an infrared-transmitting filter, examples of the infrared-transmitting filter include a filter which blocks visible light and transmits light having a wavelength of 900nm or more. When the film of the present invention is used as an infrared transmission filter, a filter including a composition of a near-infrared absorbing compound and a color material for shielding visible light (preferably, a color material containing two or more color colorants or a color material containing at least an organic black colorant), or a filter including a layer containing a near-infrared absorbing compound and a layer containing another color material for shielding visible light is preferably used. When the film of the present invention is used as an infrared transmission filter, the near-infrared absorbing compound has a function of limiting light (near-infrared) to be transmitted to a longer wavelength side.
The thickness of the film of the present invention can be appropriately adjusted as needed. The film thickness is preferably 20 μm or less, more preferably 10 μm or less, and further preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and further preferably 0.3 μm or more.
The films of the present invention can also be used in combination with color filters containing colored colorants. For example, the film of the present invention can be used as a laminate by laminating a color filter. In the laminate, the film of the present invention and the color filter may or may not be adjacent to each other in the thickness direction. When the film of the present invention and the color filter are adjacent in the thickness direction, the film of the present invention may be formed on a support different from the support on which the color filter is formed, and other components (for example, a microlens, a planarizing layer, and the like) constituting the solid-state imaging element may be sandwiched between the film of the present invention and the color filter. The color filter can be manufactured by using a coloring composition including a colored colorant. The colored colorant may be the one described as the composition of the present invention.
In the present invention, the near-infrared cut filter is a filter that transmits light having a wavelength in the visible region (visible light) and blocks at least a part of light having a wavelength in the near-infrared region (near-infrared light). The near-infrared cut filter may completely transmit light having a wavelength in the visible region, or may transmit light having a specific wavelength region among light having a wavelength in the visible region and block light having a specific wavelength region. In the present invention, the color filter is a filter that transmits light of a specific wavelength region among light of wavelengths in the visible region and blocks light of the specific wavelength region. The infrared transmission filter is a filter that shields light having a wavelength in the visible region and transmits at least a part of light having a wavelength in the near-infrared region (near-infrared rays).
When the film of the present invention is used as a near infrared ray cut filter, the film of the present invention preferably has an absorption maximum wavelength in a wavelength range of 700 to 1000 nm. The average transmittance at a wavelength of 400 to 550nm is preferably 70% or more, more preferably 80% or more, further preferably 85% or more, and particularly preferably 90% or more. The transmittance in the entire wavelength range of 400 to 550nm is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more. The near-infrared shielding property of the near-infrared cut filter is preferably in a range of 20% or less, more preferably 15% or less, and even more preferably 10% or less, in at least one region having a wavelength of 700 to 1000nm, depending on the application.
When the film of the present invention is used as an infrared transmission filter, the maximum value of the transmittance of the film of the present invention in the thickness direction of the film in the range of wavelengths of 400 to 830nm is 20% or less, and the minimum value of the transmittance of the film in the thickness direction of the film in the range of wavelengths of 1000 to 1300nm is preferably 80% or more. The film having these spectral characteristics can be preferably used as an infrared transmission filter that shields light having a wavelength of 400 to 750nm and transmits light having a wavelength of 900nm or more.
The film of the present invention can be used in various devices such as a solid-state imaging element such as a CCD (charge coupled device) or a CMOS (complementary metal oxide semiconductor), an infrared sensor, and an image display device.
< method for producing film >
Next, a method for producing a film of the present invention will be described. The film of the present invention can be produced through a process of coating the composition of the present invention.
In the method for producing a film of the present invention, the composition is preferably applied to a support. Examples of the support include a substrate made of a material such as silicone, alkali-free glass, soda glass, PYREX (registered trademark) glass, or quartz glass. An organic film, an inorganic film, or the like may be formed on these substrates. Examples of the material of the organic film include the resins described in the column of the above-mentioned composition. As the support, a substrate made of resin may be used. A Charge Coupled Device (CCD), a Complementary Metal Oxide Semiconductor (CMOS), a transparent conductive film, or the like may be formed on the support. Further, a black matrix for separating the pixels may be formed on the support. The substrate may be provided with an undercoat layer, if necessary, for improving adhesion to the upper layer, preventing diffusion of a substance, or flattening the surface of the substrate. When a glass substrate is used as the support, it is preferable to form an inorganic film on the glass substrate or to use the glass substrate after dealkalization.
As a method for applying the composition, a known method can be used. Examples thereof include: dropping method (drop coating); slit coating method; spraying; a roll coating method; spin coating (spin coating); tape casting coating method; slit and spin methods; a prewet method (for example, the method described in Japanese patent laid-open No. 2009-145395); various printing methods such as discharge printing such as ink jet printing (for example, on-demand spray printing, piezoelectric printing, and thermal printing), nozzle spray printing, flexographic printing, screen printing, gravure printing, reverse offset printing, and metal mask printing; transfer methods using a mold or the like, nanoimprint methods, and the like. The method of applying the ink jet is not particularly limited, and examples thereof include a method (particularly from 115 to 133 pages) described in "unlimited possibility of spreading and using ink jet-patent", published in 2.2005, sumibe Techon Research co., ltd. ", and a method described in japanese patent application laid-open nos. 2003-262716, 2003-185831, 2003-261827, 2012-126830, and 2006-1699325.
The composition layer formed by coating the composition may be dried (prebaked). In the case of forming a pattern by a low-temperature process, pre-baking may not be performed. When the prebaking is performed, the prebaking temperature is preferably 150 ℃ or lower, more preferably 120 ℃ or lower, and further preferably 110 ℃ or lower. The lower limit can be, for example, 50 ℃ or higher, and can also be 80 ℃ or higher. When the photoelectric conversion film of the image sensor is formed of, for example, an organic material, these characteristics can be further effectively maintained by performing the prebaking at a temperature of 150 ℃.
The prebaking time is preferably 10 seconds to 3000 seconds, more preferably 40 seconds to 2500 seconds, and further preferably 80 seconds to 220 seconds. Drying may be carried out by a hot plate, oven.
The film production method of the present invention may further include a step of forming a pattern. As the pattern forming method, a pattern forming method using photolithography is preferable. The pattern forming method by photolithography preferably includes the steps of: an exposure step of exposing a composition layer formed by applying the composition of the present invention in a pattern; and a developing step of developing and removing the composition layer in the unexposed portion to form a pattern. If necessary, a step of baking the developed pattern (post-baking) may be provided. Hereinafter, each step will be explained.
In the exposure step, the composition layer is exposed in a pattern. For example, the composition layer can be pattern-exposed by exposing the composition layer through a mask having a predetermined mask pattern using an exposure device such as a stepper. Thereby, the exposed portion can be cured. As the radiation (light) that can be used in the exposure, ultraviolet rays such as g-rays and i-rays are preferable, and i-rays are more preferable. The dose (exposure) is preferably 0.03 to 2.5J/cm2More preferably 0.05 to 1.0J/cm2Most preferably 0.08 to 0.5J/cm2. The oxygen concentration at the time of exposure can be appropriately selected, and in addition to the atmospheric air, for example, exposure may be performed in a low oxygen environment (for example, 15 vol%, 5 vol%, substantially no oxygen) in which the oxygen concentration is 19 vol% or less, or exposure may be performed in a high oxygen environment (for example, 22 vol%, 30 vol%, 50 vol%) in which the oxygen concentration is more than 21 vol%. The exposure illuminance can be set as appropriate, and can be selected from 1000W/m in general2～100000W/m2(e.g., 5000W/m)2、15000W/m2、35000W/m2) The range of (1). The oxygen concentration and the exposure illumination may be combined under appropriate conditions, and for example, the oxygen concentration may be 10 vol% and the illumination may be 10000W/m2Oxygen concentration of 35 vol% and illuminance of 20000W/m2And the like.
Then, the composition layer of the unexposed portion in the exposed composition layer is removed by development to form a pattern. The composition layer of the unexposed portion can be removed by development using a developer. In this way, the composition layer in the unexposed portion in the exposure step is eluted by the developer, and only the photocured portion remains on the support. As the developing solution, an alkali developing solution which does not damage a solid-state imaging element, a circuit, or the like of a substrate is preferable. The temperature of the developing solution is preferably 20 to 30 ℃. The developing time is preferably 20 to 180 seconds. Further, in order to improve the residue removal property, a process of throwing off the developer every 60 seconds and supplying a new developer may be repeatedly performed a plurality of times.
Examples of the alkaline agent used in the developer include organic alkaline compounds such as ammonia, ethylamine, diethylamine, dimethylethanolamine, diethyleneglycol amine, diethanolamine, hydroxylamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, and 1, 8-diazabicyclo [5,4,0] -7-undecene, and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, and sodium metasilicate. The developer may preferably use an alkaline aqueous solution in which these alkaline agents are diluted with pure water. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. The developer may contain a surfactant. Examples of the surfactant include the surfactants described in the above-mentioned composition, and nonionic surfactants are preferable. The developer can be once produced as a concentrated solution from the viewpoint of convenience in transportation and storage, and diluted to a desired concentration when used. The dilution ratio is not particularly limited, and can be set, for example, in the range of 1.5 to 100 times. In addition, when a developer including these alkaline aqueous solutions is used, it is preferable to wash (rinse) with pure water after development.
After the development, a heat treatment (post-baking) can be performed after the drying. The post-baking is a post-development heat treatment for completely curing the film. When post-baking is performed, the post-baking temperature is preferably 100 to 240 ℃. From the viewpoint of film curing, it is more preferably 200 to 230 ℃. When an organic electroluminescence (organic EL) element is used as a light source for emitting light or when a photoelectric conversion film of an image sensor is formed from an organic material, the post-baking temperature is preferably 150 ℃ or lower, more preferably 120 ℃ or lower, still more preferably 100 ℃ or lower, and particularly preferably 90 ℃ or lower. The lower limit can be set to 50 ℃ or higher, for example. The post-baking of the developed film can be performed continuously or intermittently by a heating mechanism such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater so as to satisfy the above conditions. Also, in the case of forming a pattern by a low temperature process, post baking may not be performed.
< near infrared ray cut filter >
Next, the near-infrared cut filter of the present invention will be described. The near-infrared cut filter of the present invention has the film of the present invention.
The near-infrared cut filter of the present invention may have a copper-containing layer, a dielectric multilayer film, an ultraviolet absorbing layer, and the like, in addition to the film of the present invention. The near-infrared cut filter of the present invention further includes a layer containing copper and/or a dielectric multilayer film, and thus a wide viewing angle and a near-infrared cut filter having excellent near-infrared shielding properties can be easily obtained. Further, the near-infrared cut filter of the present invention further includes an ultraviolet absorbing layer, and thus can be a near-infrared cut filter having excellent ultraviolet shielding properties. For example, the ultraviolet absorbing layer described in paragraphs 0040 to 0070 and 0119 to 0145 of International publication WO2015/099060 can be referred to and incorporated herein. Reference is made to the description of paragraphs 0255 to 0259 of japanese patent application laid-open No. 2014-041318 as a dielectric multilayer film, and the contents thereof are incorporated in the present specification. As the copper-containing layer, a glass substrate made of copper-containing glass (copper-containing glass substrate) or a copper-containing complex layer (copper-containing complex layer) can be used. Examples of the copper-containing glass substrate include copper-containing phosphate glass and copper-containing fluorophosphate glass. Commercially available copper-containing glasses include NF-50 (manufactured by AGC TECHNO GLASS CO., LTD.), BG-60, BG-61 (manufactured by Schott AG), CD5000 (manufactured by HOYA GROUP), and the like.
The near-infrared cut filter of the present invention can be used in various devices such as a solid-state imaging device such as a CCD (charge coupled device) or a CMOS (complementary metal oxide semiconductor), an infrared sensor, and an image display device.
The near-infrared cut filter of the present invention is also a preferable embodiment having pixels (patterns) of the film obtained using the composition of the present invention and pixels (patterns) selected from the group consisting of red, green, blue, magenta, yellow, cyan, black and colorless.
< solid-state imaging element >
The solid-state imaging element of the present invention includes the film of the present invention. The structure of the solid-state imaging element is not particularly limited as long as it has the film of the present invention and functions as a solid-state imaging element. For example, the following structures can be mentioned.
The structure is as follows: the solid-state imaging device includes a support, a transfer electrode including a plurality of photodiodes and polysilicon constituting a light receiving area of the solid-state imaging element, a light shielding film including tungsten and the like and having openings only for light receiving portions of the photodiodes, the light shielding film including a device protection film including silicon nitride and the like and formed so as to cover the entire light shielding film and the light receiving portions of the photodiodes, and the device protection film including the film of the present invention. Further, the device protective film may be provided with a light condensing means (for example, a microlens) on the lower side (side close to the support) of the film in the present invention, or the film in the present invention may be provided with a light condensing means. Also, the color filter may have the following structure: a film for forming each pixel is embedded in a space divided into, for example, a lattice shape by a partition wall. In this case, the refractive index of the partition wall is preferably lower than that of each pixel. Examples of imaging devices having these structures include those described in japanese patent laid-open nos. 2012 and 227478 and 2014 and 179577.
< image display device >
The image display device of the present invention includes the film of the present invention. Examples of the image display device include a liquid crystal display device and an organic electroluminescence (organic EL) display device. The definition and details of the image display device are described in, for example, "electronic display device (published in zozuki shoff, Kogyo Chosakai Publishing co., ltd.1990)", "display device (published in yichu, Sangyo Tosho Publishing co., ltd.1989)", and the like. Further, the liquid crystal display device is described in, for example, "next generation liquid crystal display technology (edited by tianda male, published by the industrial research society in 1994)". The liquid crystal display device to which the present invention can be applied is not particularly limited, and for example, the present invention can be applied to liquid crystal display devices of various types described in the above-mentioned "next generation liquid crystal display technology". The image display device may have a white organic EL element. As the white organic EL element, a tandem structure is preferable. The tandem structure of organic EL elements is described in japanese patent application laid-open No. 2003-045676, the third best practice, "the first line of development of organic EL technology — high brightness, high precision, long lifetime, technical secret-dense", the association of technical information, page 328, 2008, and the like. The spectrum of white light emitted from the organic EL element preferably has strong maximum emission peaks in the blue region (430nm-485nm), green region (530nm-580nm), and yellow region (580nm-620 nm). In addition to these emission peaks, it is more preferable to further have a maximum emission peak in a red region (650nm to 700 nm).
< Infrared sensor >
The infrared sensor of the present invention comprises the film of the present invention described above. The structure of the infrared sensor is not particularly limited as long as it can function as an infrared sensor. Hereinafter, an embodiment of the infrared sensor according to the present invention will be described with reference to the drawings.
In fig. 1, reference numeral 110 denotes a solid-state imaging element. The near infrared ray cut filter 111 and the infrared ray transmission filter 114 are provided in an imaging region provided on the solid-state imaging element 110. A color filter 112 is laminated on the near-infrared cut filter 111. A microlens 115 is disposed on the incident light hv side of the color filter 112 and the infrared transmission filter 114. A planarization layer 116 is formed so as to cover the microlenses 115.
The near-infrared cut filter 111 can be formed using the composition of the present invention. The spectral characteristics of the near infrared ray cut filter 111 may be selected according to the emission wavelength of the infrared light emitting diode (infrared LED) used.
The color filter 112 is a color filter in which pixels that transmit and absorb light of a specific wavelength in the visible region are formed, and is not particularly limited, and conventionally known color filters for forming pixels can be used. For example, a color filter or the like in which pixels of red (R), green (G), and blue (B) are formed may be used. For example, reference may be made to the descriptions in paragraphs 0214 to 0263 of japanese patent application laid-open No. 2014-043556, and the contents thereof are incorporated in the present specification.
The infrared transmission filter 114 has characteristics selected according to the emission wavelength of the infrared LED used. For example, when the emission wavelength of the infrared LED is 850nm, the maximum value of the transmittance of the infrared transmission filter 114 in the thickness direction of the film in the wavelength range of 400 to 650nm is preferably 30% or less, more preferably 20% or less, further preferably 10% or less, and particularly preferably 0.1% or less. The transmittance preferably satisfies the above condition in all regions of the wavelength range of 400 to 650 nm.
The minimum value of the light transmittance of the infrared transmission filter 114 in the thickness direction of the film in the range of a wavelength of 800nm or more (preferably 800 to 1300nm) is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more. The transmittance preferably satisfies the above condition in a part of the range of 800nm or more, and preferably satisfies the above condition at a wavelength corresponding to the emission wavelength of the infrared LED.
The film thickness of the infrared transmission filter 114 is preferably 100 μm or less, more preferably 15 μm or less, still more preferably 5 μm or less, and particularly preferably 1 μm or less. The lower limit is preferably 0.1. mu.m. If the film thickness is within the above range, the film can satisfy the spectral characteristics.
The following describes a method for measuring the spectral characteristics, film thickness, and the like of the infrared transmission filter 114.
The film thickness was measured using a stylus-type surface texture measuring instrument (ULVAC, DEKTAK150, inc.) on a substrate after drying having a film.
The spectral characteristics of the film are values obtained by measuring the transmittance at a wavelength of 300 to 1300nm using an ultraviolet-visible near-infrared spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation).
Further, for example, when the emission wavelength of the infrared LED is 940nm, the maximum value of the transmittance of the infrared transmission filter 114 in the film thickness direction for light having a wavelength of 450 to 650nm is 20% or less, the transmittance of the infrared transmission filter 114 in the film thickness direction for light having a wavelength of 835nm is 20% or less, and the minimum value of the transmittance of the infrared transmission filter 114 in the film thickness direction for light having a wavelength of 1000 to 1300nm is preferably 70% or more.
In the infrared sensor shown in fig. 1, a near infrared ray cut filter (another near infrared ray cut filter) different from the near infrared ray cut filter 111 may be disposed on the planarization layer 116. Examples of other near-infrared cut filters include a copper-containing layer and/or a near-infrared cut filter having a dielectric multilayer film. The details of these are as described above. As another near infrared ray cut filter, a dual band bandpass filter may be used.
Detailed Description
The present invention will be described in further detail below with reference to examples. The materials, the amounts used, the ratios, the contents of the processes, the processing procedures, and the like described in the following examples can be appropriately modified without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "part" and "%" are based on mass.
< determination of weight average molecular weight >
The weight average molecular weights of compound a and the resin were measured by Gel Permeation Chromatography (GPC) under the following conditions.
The types of the pipe columns are as follows: a pipe column formed by connecting TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000 and TOSOH TSKgel Super HZ2000
Developing solvent: tetrahydrofuran (THF)
Temperature of the pipe column: 40 deg.C
Flow rate (sample injection amount): 1.0. mu.L (sample concentration: 0.1 mass%)
Device name: HLC-8220GPC made by TOSOH CORPORATION
A detector: RI (refractive index) detector
Calibration curve base resin: polystyrene resin
< method for measuring acid value >
The acid values of the compound A and the resin indicate the mass of potassium hydroxide required for neutralizing 1g of the acidic component in the solid content. The acid values of compound a and the resin were measured as follows. Specifically, a measurement sample was dissolved in a mixed solvent of tetrahydrofuran and water (mass ratio) 9/1, and the resulting solution was subjected to neutralization titration with a 0.1mol/L aqueous solution of sodium hydroxide AT 25 ℃ using a potentiometric titrator (trade name: AT-510, manufactured by KYOTO ELECTRONICS MANUFACTURING CO., LTD.). The inflection point of the titration pH curve was taken as the titration end point, and the acid value was calculated by the following formula.
A＝56.11×Vs×0.5×f/w
A: acid value (mgKOH/g)
Vs: amount of 0.1mol/L aqueous sodium hydroxide solution (mL) required for titration
f: titer of 0.1mol/L aqueous sodium hydroxide solution
w: measurement of sample Mass (g) (conversion of solid content)
Determination of the value of < C ═ C >
The C ═ C value of compound a indicates the molar amount of C ═ C groups per 1g of the solid content of compound a, and the low molecular weight component (a) at the C ═ C group position (for example, methacrylic acid in P-1 and acrylic acid in P-2 described above) was extracted from compound a by alkali treatment, and the content thereof was measured by High Performance Liquid Chromatography (HPLC), and calculated from the following formula. Specifically, 0.1g of the measurement sample was dissolved in 50mL/15mL of tetrahydrofuran/methanol, and 10mL of a 4mol/L aqueous sodium hydroxide solution was added to the solution to react at 40 ℃ for 2 hours. The reaction solution was neutralized with 10.2mL of a 4mol/L methanesulfonic acid aqueous solution, and then a mixed solution containing 5mL of ion-exchanged water and 2mL of methanol was transferred to a 100mL volumetric flask, and a HPLC measurement sample was prepared by diluting the volume with methanol and measured under the following conditions. The content of the low-molecular component (a) is calculated from a calibration curve of the low-molecular component (a) prepared separately, and the value of C ═ C is calculated by the following formula.
Calculation of < C ═ C value
C ═ C value [ mmol/g ] (content of low-molecular component (a) [ ppm ]/molecular weight of low-molecular component (a) [ g/mol ])/(weighed value of liquid-adjusting polymer [ g ] × (solid content concentration of polymer liquid [% ]/100) × 10)
< HPLC measurement conditions >
Measurement machine: agilent-1200
Pipe column: synergi 4u Polar-RP 80A manufactured by Phenomenex, 250mm multiplied by 4.60mm (inner diameter) + protective pipe column
Temperature of the pipe column: 40 deg.C
Analysis time: 15 minutes
Flow rate: 1.0 mL/min (maximum delivery pressure: 182bar)
Injection amount: 5 μ l
Detection wavelength: 210nm
Eluent: tetrahydrofuran (for HPLC without stabilizer)/buffer solution (ion-exchanged water solution containing 0.2 vol% of phosphoric acid and 0.2 vol% of triethylamine) ═ 55/45 (vol%)
[ test example 1]
< preparation of Dispersion >
After mixing the raw materials described in the following table, 230 parts by mass of zirconia beads having a diameter of 0.3mm were added, and dispersion treatment was performed for 5 hours using a paint shaker, and the beads were filtered and separated to prepare a dispersion. The numerical values shown in the following tables are parts by mass. The numerical values of the parts by mass described in the columns for the near-infrared absorbing compound, the derivative, and the dispersant are values of the solid content.
< evaluation of stability with time >
The viscosity of the obtained dispersion liquid immediately after production was measured. The dispersion having the measured viscosity was stored in a thermostatic bath at 45 ℃ for 72 hours, and then the viscosity was measured. The temperature of the dispersion was adjusted to 23 ℃ and the viscosity was measured. The thickening efficiency was calculated from the following calculation formula, and the stability over time was evaluated.
Viscosity increase ratio (%) ((viscosity of dispersion stored at 45 ℃ for 72 hours/viscosity of dispersion immediately after production) -1) × 100
[ Table 8]
Figure BDA0002147187970000711
As shown in the above table, the dispersions of examples 1 to 9 had a low thickening ratio and excellent stability over time.
< preparation of curable composition >
The raw materials described in the following table were mixed to prepare a curable composition. The numerical values shown in the following tables are parts by mass. The numerical values of the parts by mass described in the columns of the near-infrared absorbing compound, the color colorant, the dispersant, the resin, the polymerizable compound, the ultraviolet absorber, the surfactant, the polymerization inhibitor, and the antioxidant are values of the solid content. In addition, a dispersion prepared as follows was used for the curable composition using the dispersion B. A color colorant, a dispersant and a solvent of the kind described in the column of dispersion B in the following table were mixed in the parts by mass described in the column of dispersion B, and 230 parts by mass of zirconia beads having a diameter of 0.3mm were further added, and dispersion treatment was performed for 5 hours using a paint shaker, and the beads were filtered and separated to produce dispersion B.
< evaluation of adhesion >
A silicon wafer was coated with CT-4000 (made by FUJIFILM Electronic Materials co., ltd.) by a spin coating method so that the thickness of the film became 0.1 μm, and heated at 220 ℃ for 1 hour using a hot plate to form an underlayer. A silicon wafer with this underlayer was coated with a curable composition by a spin coating method, and then heated at 100 ℃ for 2 minutes using a hot plate to obtain a composition layer having a film thickness shown in the following table.
The composition layer was irradiated with 365nm wavelength light through a mask pattern of 4mm × 3mm regions in which square pixels each having a side of 1.1 μm were arranged on a substrate using an i-ray stepper FPA-3000i5+ (manufactured by Canon Inc.) and exposed to an exposure of 500mJ/cm2The exposure is performed.
The composition layer after exposure was subjected to stirring development at 23 ℃ for 60 seconds using a 0.3 mass% aqueous solution of tetramethylammonium hydroxide. Then, the film was washed with water by rotating spray, and further washed with pure water. Then, after discharging water droplets under high pressure air and naturally drying the silicon wafer, post-baking was performed at 220 ℃ for 300 seconds using a hot plate, thereby forming a pattern. The obtained patterns were observed with an optical microscope, and the number of patterns adhered to each other was counted in the total pattern to evaluate the adhesion.
5: all patterns were closed.
4: the pattern is more than 90% and less than 100% of the total pattern.
3: the pattern is more than 80% and less than 90% of the total pattern.
2: the pattern is 70% or more and less than 80% of the total pattern.
1: the pattern sealed is less than 70% of the total pattern.
Figure BDA0002147187970000731
As shown in the above table, the examples had excellent adhesion.
The raw materials listed in the above table are as follows.
(near-infrared ray-absorbing Compound)
A1-A6: a compound of the structure. In the following structural formula, Me represents a methyl group, and Ph represents a phenyl group.
[ chemical formula 34]
Figure BDA0002147187970000741
(pigment derivative)
B1-B3: a compound of the structure. In the following structural formula, Me represents a methyl group, and Ph represents a phenyl group.
[ chemical formula 35]
Figure BDA0002147187970000751
(dispersing agent)
P-1 to P-8, P-16: specific examples of the above-mentioned compound A include P-1 to P-8 and P-16.
Dispersant 1: a resin having the following structure (the numerical values indicated in the main chain are molar ratios, and the numerical values indicated in the side chain are repeating units. Mw ═ 20,000)
[ chemical formula 36]
Figure BDA0002147187970000761
Dispersant 2: a resin having the following structure. (the values indicated in the main chain are molar ratios and the values indicated in the side chain are repeating units. Mw. about.11,000)
[ chemical formula 37]
Figure BDA0002147187970000762
(color colorant)
PR254：C.I.Pigment Red 254
PB15:6：C.I.Pigment Blue 15:6
PY139：C.I.Pigment Yellow 139
(resin)
D1: a resin having the following structure. (the numerical values indicated in the main chain are molar ratio, Mw 40,000, acid value 100mgKOH/g)
D2: a resin having the following structure. (the values indicated in the main chain are molar ratio. Mw 10,000, acid value 70mgKOH/g)
[ chemical formula 38]
Figure BDA0002147187970000763
(polymerizable Compound)
E1: ARONIX M-305(TOAGOSEI CO., LTD. manufactured)
E2: NK ester A-TMMT (Shin-Nakamura Chemical CO., LTD., manufactured by Ltd.)
E3: KAYARAD DPHA (Nippon Kayaku Co., Ltd.)
E4: ARONIX M-510(TOAGOSEI CO., LTD. manufactured)
(photopolymerization initiator)
F1: IRGACURE OXE02 (manufactured by BASF corporation)
F2: IRGACURE 369 (manufactured by BASF corporation)
F3: IRGACURE OXE03 (manufactured by BASF corporation)
(ultraviolet absorber)
G1, G2: a compound of the structure
[ chemical formula 39]
Figure BDA0002147187970000771
(surfactant)
H1: the following mixture (Mw 14000, fluorine surfactant). In the following formula,% indicating the proportion of the repeating unit is mass%.
[ chemical formula 40]
Figure BDA0002147187970000772
(polymerization inhibitor)
I1: p-methoxyphenol
(antioxidant)
J1: adekastab AO-80 (manufactured by ADEKA CORPORATION)
(solvent)
PGMEA: propylene glycol monomethyl ether acetate
[ test example 2]
The curable compositions of examples 101 to 109 were coated on a silicon wafer by a spin coating method so that the film thickness after deposition became 1.0. mu.m. Next, the mixture was heated at 100 ℃ for 2 minutes using a hot plate. Next, an i-ray stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.) was used at 1000mJ/cm2The exposure amount of (2) was exposed through a mask having a2 μm square Bayer pattern.
Next, stirring (paddle) development was performed at 23 ℃ for 60 seconds using a 0.3 mass% aqueous solution of tetramethylammonium hydroxide (TMAH). Thereafter, the film was washed by rotary shower, and further washed by pure water. Next, the resultant was heated at 200 ℃ for 5 minutes using a hot plate to form a2 μm square Bayer pattern (near infrared ray cut filter).
Next, the Red composition was applied on the Bayer pattern of the near-infrared cut filter by a spin coating method so that the film thickness after film formation became 1.0 μm. Next, the plate was heated at 100 ℃ for 2 minutes using a hot plate. Next, an i-ray stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.) was used at 1000mJ/cm2Is exposed through a mask having a2 μm square Bayer pattern. Next, stirring (paddle) development was performed at 23 ℃ for 60 seconds using a 0.3 mass% aqueous solution of tetramethylammonium hydroxide (TMAH). Thereafter, the film was washed by rotary shower, and further washed by pure water. Next, the Red composition was patterned on the Bayer pattern of the near infrared ray cut filter by heating at 200 ℃ for 5 minutes using a hot plate. Similarly, the Green composition and the Blue composition are patterned in sequence to form red, Green, and Blue colored patterns.
Then, the infrared transmission filter forming group was spin-coated so that the film thickness after film formation became 2.0 μmThe composition is coated on the patterned film. Next, the plate was heated at 100 ℃ for 2 minutes using a hot plate. Next, an i-ray stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.) was used at 1000mJ/cm2The exposure amount of (b) was exposed via a mask having a2 μm square Bayer pattern. Next, stirring (paddle) development was performed at 23 ℃ for 60 seconds using a 0.3 mass% aqueous solution of tetramethylammonium hydroxide (TMAH). Thereafter, the film was washed by rotary shower, and further washed by pure water. Next, the Bayer pattern defect portion of the near infrared ray cut filter was patterned with an infrared ray transmission filter by heating at 200 ℃ for 5 minutes using a hot plate. The solid-state imaging element is assembled according to these known methods.
The obtained solid-state imaging device was evaluated for image performance by irradiating light from an infrared light-emitting diode (infrared LED) light source under a low-illuminance environment (0.001Lux) and reading an image. The subject is clearly observed on the image. Further, the incident angle dependence is good.
The Red composition, Green composition, Blue composition and composition for forming an infrared transmission filter used in test example 2 were as follows.
(Red composition)
After mixing and stirring the following components, the mixture was filtered through a nylon filter (NIHON PALL LTD) having a pore size of 0.45. mu.m, to prepare a Red composition.
Red pigment dispersion … … 51.7.7 parts by mass
0.6 part by mass of resin 104 … … 0.6
Polymerizable compound 104 … … 0.6.6 parts by mass
Photopolymerization initiator 101 … … 0.4.4 parts by mass
Surfactant 101 … … 4.2.2 parts by mass
… … 0.3.3 parts by mass of ultraviolet absorber (UV-503, DAITO CHEMICAL CO., LTD., manufactured by LTD.) - … …
PGMEA … … 42.6.6 parts by mass
(Green composition)
The following ingredients were mixed and stirred, and then filtered through a nylon filter (manufactured by NIHON PALL LTD.) having a pore size of 0.45. mu.m, to prepare a Green composition.
… … 73.7.7 parts by mass of Green pigment dispersion liquid
0.3 part by mass of resin 104 … … 0.3
Polymerizable compound 101 … … 1.2.2 parts by mass
Photopolymerization initiator 101 … … 0.6.6 parts by mass
Surfactant 101 … … 4.2.2 parts by mass
… … 0.5.5 parts by mass of an ultraviolet absorber (UV-503, DAITO CHEMICAL CO., LTD., manufactured by LTD.) as an active ingredient
PGMEA … … 19.5.5 parts by mass
(Blue composition)
The following ingredients were mixed and stirred, and then filtered through a nylon filter (manufactured by NIHON PALL LTD.) having a pore size of 0.45. mu.m, to prepare a Blue composition.
… … 44.9.9 parts by mass of Blue pigment dispersion
Resin 104 … … 2.1.1 parts by mass
Polymerizable compound 101 … … 1.5.5 parts by mass
Polymerizable compound 104 … … 0.7.7 parts by mass
Photopolymerization initiator 101 … … 0.8.8 parts by mass
Surfactant 101 … … 4.2.2 parts by mass
… … 0.3.3 parts by mass of ultraviolet absorber (UV-503, DAITO CHEMICAL CO., LTD., manufactured by LTD.) - … …
PGMEA … … 45.8.8 parts by mass
(composition for Forming Infrared transmitting Filter)
The following components were mixed and stirred, and then filtered through a nylon filter (manufactured by NIHON PALL LTD.) having a pore size of 0.45. mu.m, to prepare a composition for forming an infrared transmission filter.
1-1 … … 46.5.5 parts by mass of pigment dispersion
1-2 parts by mass of pigment dispersion liquid 2 … … 37.1.1
Polymerizable compound 105 … … 1.8.8 parts by mass
Resin 104 … … 1.1.1 parts by mass
Photopolymerization initiator 102 … … 0.9.9 parts by mass
Surfactant 101 … … 4.2.2 parts by mass
… … 0.001.001 parts by mass of polymerization inhibitor (p-methoxyphenol)
Silane coupling agent … … 0.6.6 parts by mass
PGMEA … … 7.8.8 parts by mass
The raw materials used for the Red composition, Green composition, Blue composition and composition for forming an infrared transmission filter are as follows.
Red pigment Dispersion
A mixed solution containing 9.6 parts by mass of c.i. pigment Red 254, 4.3 parts by mass of c.i. pigment Yellow 139, 6.8 parts by mass of a dispersant (Disperbyk-161, manufactured by BYK Chemie) and 79.3 parts by mass of PGMEA was mixed and dispersed for 3 hours by a bead mill (zirconia beads having a diameter of 0.3 mm), thereby preparing a pigment dispersion. Then, a high-pressure disperser NANO-3000-10 (manufactured by Nippon Bee Chemical Co., Ltd.) having a pressure reducing mechanism was further used at 2000kg/cm3Was subjected to dispersion treatment at a flow rate of 500 g/min under pressure of (1). This dispersion treatment was repeated 10 times to obtain a Red pigment dispersion.
Green pigment Dispersion
A mixed solution containing 6.4 parts by mass of c.i. pigment Green 36, 5.3 parts by mass of c.i. pigment Yellow 150, 5.2 parts by mass of a dispersant (Disperbyk-161, manufactured by BYK Chemie) and 83.1 parts by mass of PGMEA was mixed and dispersed for 3 hours by a bead mill (zirconia beads having a diameter of 0.3 mm), thereby preparing a pigment dispersion. Then, a high-pressure disperser NANO-3000-10 (manufactured by Nippon Bee Chemical Co., Ltd.) having a pressure reducing mechanism was further used at 2000kg/cm3Was subjected to dispersion treatment at a flow rate of 500 g/min under pressure of (1). This dispersion treatment was repeated 10 times to obtain a Green pigment dispersion.
Blue pigment Dispersion
A mixture containing 9.7 parts by mass of C.I.pigment Blue 15:6, 2.4 parts by mass of C.I.pigment Violet 23, 5.5 parts by mass of a dispersant (Disperbyk-161, BYK Chemie) and 82.4 parts by mass of a dispersant (BYK Chemie) was milled with a bead mill (zirconia beads having a diameter of 0.3 mm)The mixed liquid of the PGMEA parts was mixed and dispersed for 3 hours, thereby preparing a pigment dispersion liquid. Then, a high-pressure disperser NANO-3000-10 (manufactured by Nippon Bee Chemical Co., Ltd.) having a pressure reducing mechanism was further used at 2000kg/cm3Was subjected to dispersion treatment at a flow rate of 500 g/min under pressure of (1). This dispersion treatment was repeated 10 times to obtain a Blue pigment dispersion.
Pigment Dispersion 1-1
The pigment dispersion liquid 1-1 was prepared by mixing and dispersing a mixed liquid of the following composition for 3 hours using zirconia beads having a diameter of 0.3mm by a bead mill (high pressure disperser NANO-3000-10(Nippon be Chemical co., ltd.) with a decompression mechanism).
Mixed pigment … … 11.8.8 parts by mass, which contains a Red pigment (c.i. pigment Red 254) and a Yellow pigment (c.i. pigment Yellow 139)
… … 9.1.1 parts by mass of resin (Disperbyk-111, BYK Chemie Co., Ltd.)
PGMEA … … 79.1.1 parts by mass
Pigment Dispersion 1-2
The pigment dispersion liquid 1-2 was prepared by mixing and dispersing a mixed liquid of the following composition for 3 hours using zirconia beads having a diameter of 0.3mm by a bead mill (high pressure disperser NANO-3000-10(Nippon be Chemical co., ltd.) with a decompression mechanism).
Mixed pigment … … 12.6.6 parts by mass, which contains Blue pigment (c.i. pigment Blue 15:6) and Violet pigment (c.i. pigment Violet 23)
… … 2.0.0 parts by mass of resin (Disperbyk-111, BYK Chemie Co., Ltd.)
Resin A … … 3.3.3 parts by mass
… … 31.2.2 parts by mass of Cyclohexanone
50.9 parts by mass of PGMEA … … 50.9
Resin A: a resin having the following structure (Mw: 14,000, ratio in structural units is molar ratio)
[ chemical formula 41]
Figure BDA0002147187970000821
Polymerizable compound 101: KAYARAD DPHA (Nippon Kayaku Co., Ltd.)
Polymerizable compound 104: a compound of the structure
[ chemical formula 42]
Figure BDA0002147187970000822
Polymerizable compound 105: mixture of the following structures (mixture of the left compound and the right compound in a molar ratio of 7: 3)
[ chemical formula 43]
Figure BDA0002147187970000823
Resin 104: a resin having the following structure (acid value: 70mgKOH/g, Mw 11000, molar ratio in structural units)
[ chemical formula 44]
Figure BDA0002147187970000831
Photopolymerization initiator 101: IRGACURE-OXE01 (manufactured by BASF corporation)
Photopolymerization initiator 102: a compound of the structure
[ chemical formula 45]
Figure BDA0002147187970000832
Surfactant 101: a1 mass% PGMEA solution of the following mixture (Mw 14000). In the following formula,% indicating the proportion of the repeating unit is mass%.
[ chemical formula 46]
Figure BDA0002147187970000833
Silane coupling agent: a compound of the structure. In the following structural formulae, Et represents an ethyl group.
[ chemical formula 47]
Figure BDA0002147187970000841
Description of the symbols
110-solid-state imaging element, 111-near infrared ray cut-off filter, 112-color filter, 114-infrared ray transmission filter, 115-microlens, 116-planarization layer.

Claims (15)

1. A composition comprising:
a near-infrared ray absorbing compound having a pi-conjugated plane containing a monocyclic or fused aromatic ring; and
a compound A having a radical polymerizable ethylenically unsaturated group and a weight average molecular weight of 3000 or more,
the compound A comprises a repeating unit with a grafted chain,
the radical polymerizable ethylenic unsaturated group of the compound A is at least one selected from the group consisting of a vinyl group, a vinyloxy group, an allyl group, a methallyl group, a (meth) acryloyl group, a styryl group, a cinnamoyl group, and a maleimide group,
the graft chain has a structure represented by the following formula (G-1a), formula (G-2a), formula (G-3a), formula (G-4a) or formula (G-5a),
Figure FDA0003118923910000011
in the formula (G-1a), the formula (G-2a), the formula (G-3a), the formula (G-4a) and the formula (G-5a), RG1And RG2Each independently represents an alkylene group, RG3Represents a hydrogen atom or a methyl group, QG1represents-O-or-NH-, LG1Represents a single bond or a 2-valent linking group, RG4Represents a hydrogen atom or a substituent, W100Represents a hydrogen atom or a substituent, n1 to n5 each independently represent an integer of 2 or more.
2. The composition of claim 1, wherein,
the graft chain has a structure represented by the formula (G-1a), the formula (G-4a) or the formula (G-5 a).
3. The composition of claim 1 or 2,
the repeating unit having a graft chain has a weight average molecular weight of 1000 or more.
4. The composition of claim 1 or 2,
the compound A contains a repeating unit having a radical polymerizable ethylenically unsaturated group and a repeating unit having a graft chain.
5. The composition of claim 1 or 2,
the compound A comprises a repeating unit represented by the following formula (A-1-1) and a repeating unit represented by the following formula (A-1-2);
Figure FDA0003118923910000021
in the formula (A-1-1), X1Denotes the main chain of the repeating unit, L1Represents a single bond or a 2-valent linking group, Y1A group which represents an ethylenically unsaturated group having radical polymerizability;
in the formula (A-1-2), X2Denotes the main chain of the repeating unit, L2Represents a single bond or a 2-valent linking group, W1The graft chain is shown.
6. The composition of claim 1 or 2,
the compound a further comprises a repeating unit having an acid group.
7. The composition of claim 1 or 2,
the amount of the radical polymerizable ethylenically unsaturated group in the compound A is 0.2 to 5.0 mmol/g.
8. The composition of claim 1 or 2,
the acid value of the compound A is 20 mgKOH/g-150 mgKOH/g.
9. The composition of claim 1 or 2,
the near-infrared absorbing compound is at least one selected from the group consisting of a pyrrolopyrrole compound, a cyanine compound, a squaric acid compound, a phthalocyanine compound, a naphthalocyanine compound, and a diimmonium compound.
10. The composition according to claim 1 or 2, further comprising a color material which transmits infrared rays and shields visible rays.
11. A film obtained from the composition of claim 1.
12. A near infrared ray cut filter having the film according to claim 11.
13. A solid-state imaging element having the film according to claim 11.
14. An image display device having the film according to claim 11.
15. An infrared sensor having the film of claim 11.
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